Fabric color care method for rejuvenating and/or restoring color to a faded fabric

ABSTRACT

The present invention relates to fabric care methods for restoring and/or rejuvenating color of worn, faded fabric, by applying to said fabric a fabric color care composition which comprises: water soluble and/or water dispersible polymers; surfactant capable of forming a bilayer structure; and mixtures thereof. Optionally, the composition can contain other ingredients to provide additionally fabric care benefits, and/or to improve performance and formulatability. The composition is preferably applied as small particle size droplets, especially from spray container which preferably are in association with a set of instructions for use.

This application claims benefit of Provisional application Ser. No.60/105,375 filed Oct. 23, 1998.

TECHNICAL FIELD

The present invention relates to methods and articles for treatingfabrics to improve fabric appearance, especially with regards to colorof fabrics, especially those that have been worn and having a fadedappearance.

BACKGROUND OF THE INVENTION

There is a continuous need for improved compositions, products, andmethods that provide useful benefits to fabrics, especially clothing,such as maintaining and/or improving a good appearance, especiallyfabric color, especially for fabric that have been worn, through asimple and convenient application of a product.

Consumer commonly judges the desirability and wearability of a garmentby many appearance criteria, such as, absence of color fading, absenceof wrinkles, absence of soiling and staining, absence of damage such aspilling, and the like. It is preferable that these benefits are providedvia simple and convenient consumer compositions, methods and products,to be applied in the consumer's home. These consumer compositions andproducts are preferably safe, and do not involve complicated and/orunsafe treatments and/or applications. Desirably they comprisetreatments that are familiar to the consumers, such as spraying,soaking, adding to the wash cycle, adding to the rinse cycle, and/oradding to the drying cycle.

Many published fabric care compositions methods try to provide fabricmaintenance benefits, e.g., keep fabric from, e.g., fading, wear,pilling, soiling, staining, shrinkage, and the like. However, fabricarticles, such as clothing, that are worn and used will get damaged via,e.g., mechanical abrasion in use and in the laundry washing processes.The resulting worn, damaged fabric can have loosened fabric weave andpilling. Worn, damaged color fabric especially has a undersirable fadedappearance. A common method that the consumer can practice to improveand/or restore the color of such worn, faded fabric is the use of fabricdyes. However, dyeing process done at home tend to result in colorbleeding in the subsequent washes that can discolor other fabrics in thesame wash. Furthermore, when the fabric color is not uniform, such aswhen the fabric has design with different colors and/or different tonesof the same color, the use of fabric dyes is not desirable.

The present invention comprises methods that can be used to improvecolor fidelity, i.e., recover, restore, rejuvenate color of worn,damaged clothing upon a single application.

The present invention optionally can provide other fabric care benefits,such as wrinkle removal, pill prevention, anti-shrinkage, and fabricshape retention.

SUMMARY OF THE INVENTION

The present invention relates to methods for treating fabrics by directapplication, primarily to the surface of the fabrics, of certainpreferred fabric color care actives and compositions, and to articles ofmanufacture that facilitate the use such fabric color care compositionsand other known fabric care compositions to restore and/or rejuvenatecolor of worn, faded color fabrics. The present invention also relatesto the use fabric color care active and composition comprising saidfabric color care active to restore and/or rejuvenate color of worn,faded color fabrics.

The fabric color care active that can provide the unobvious colorrestoration and/or rejuvenation benefit to the worn, faded fabric ischaracterized by its ability to reduce the three following properties ofsaid fabric, namely, its reflectance, its Hunter L value, and its pillnumber.

Preferred fabric color care composition comprises an effective amount offabric color care active preferably being selected from the groupconsisting of:

-   -   (A) water soluble and/or water dispersible polymer; said polymer        is selected from the group consisting of: natural polymer;        synthetic polymer; substituted materials thereof; derivatised        materials thereof; and mixtures thereof;    -   (B) surfactant capable of forming a bilayer structure; and    -   (C) mixtures thereof;        said composition optionally being essentially free of any        material that would soil or discernible when dried on the fabric        surface; and said composition optionally being substantially        removed during subsequent cleaning cycles to prevent undesirable        build-up of the active on the fabrics; and said composition        additionally being essentially free of any material that would        cause the treated fabric to feel unduly sticky, or “tacky” to        the touch.

Said composition is applied to fabric in a positive step, e.g.,spraying, dipping, and/or soaking processes, followed by a drying stepto maximize the application and retention of the active to the surfaceof the fibers. Preferably the treatment is by spray and/or roller sothat the active is primarily applied to the visible surface of thefabric. The present invention also preferably relates to the fabric carecompositions incorporated into a spray dispenser, to create an articleof manufacture that can facilitate treatment of fabric articles and/orsurfaces with said compositions containing fabric color care active andother optional ingredients at a level that is effective, yet ispreferably not discernible when dried on the surfaces.

Also, concentrated aqueous or solid, preferably powder, fabric colorcare compositions can be used to prepare such compositions for treatingworn, faded and/or damaged fabric.

It is especially important that said article, or any containercontaining said composition, or concentrate used to prepare saidcomposition have a set of instructions associated therewith to informthe consumer that the composition can provide the color restorationbenefit for worn, damaged and faded color fabric. Without knowledge ofthe unobvious benefit that can be obtained, a consumer would be highlyunlikely to treat the visible surface of the fabric, especially olderfabrics, and might even discard the fabric when it could besubstantially restored to near-new condition.

DETAILED DESCRIPTION OF THE INVENTION

The present invention relates to methods for treating fabrics by directapplication, primarily to the surface of the fabrics, of certainpreferred fabric color care actives and compositions, and to articles ofmanufacture that facilitate the use such fabric color care compositionsand other known fabric care compositions to restore and/or rejuvenatecolor of worn, faded color fabrics. The present invention also relatesto the use fabric color care active and composition comprising saidfabric color care active to restore and/or rejuvenate color of worn,faded color fabrics.

The unobvious color restoration and/or rejuvenation benefit to the worn,faded fabric is characterized by the ability of the fabric color careactive to change the three following properties of worn, faded blackcotton (chino) twill test fabric (as defined hereinbelow) resulting in:

-   -   (A) a percentage reflectance reduction ΔR of at least about 3%,        preferably at least about 5%, more preferably at least about 8%,        and even more preferably at least about 10%;    -   (B) a Hunter L value reduction ΔL of at least about 0.5,        preferably at least about 1.0, more preferably at least about        1.5; and even more preferably at least about 2.0; and    -   (C) a percentage pill number reduction ΔP of at least about 10%,        preferably at least about 20%, more preferably at least about        40%, and even more preferably at least about 80%.

The preferred fabric color care composition of the present inventioncomprises:

-   -   (A) an effective amount of fabric color care active for        restoring and/or rejuvenating the color of worn, faded color        fabric, said fabric color care active is preferably selected        from the group consisting of water soluble and or dispersible        polymer; substituted materials thereof; derivatised materials        thereof; and mixtures thereof; surfactant capable of forming a        bilayer structure; and mixtures thereof;    -   (B) optionally, an effective amount to provide olfactory effects        of perfume;    -   (C) optionally, to reduce surface tension and/or to improve        performance and formulatability, an effective amount of        surfactant;    -   (D) optionally, an effective amount to absorb malodor, of odor        control agent;    -   (E) optionally, an effective amount, to kill, or reduce the        growth of microbes, of antimicrobial active;    -   (F) optionally, an effective amount to provide improved        antimicrobial action of aminocarboxylate chelator;    -   (G) optionally, an effective amount of antimicrobial        preservative; and    -   (H) optionally, an aqueous carrier;        said composition optionally being essentially free of any        material that would soil or discernible when dried on the        surfaces, and said composition optionally being substantially        removed during subsequent cleaning cycles to prevent        undersirable build-up of the active on the fabrics; and said        composition additionally being essentially free of any material        that would cause the treated fabric to feel unduly sticky, or        “tacky” to the touch.

The preferred polymer is colorless, to minimize the change of hue and toimprove the color fidelity.

The present invention relates to the application of an effective amountof a fabric color care active and/or fabric color care composition tofabric to modify the following fabric properties, namely, a reduction ofreflectance, a lowering of the L value, and a reduction of themicrofibril number, to reduce the loss of fabric color and/or to recoverfabric color. It has not previously been recognized that the use of theabove compositions can provide good color restoration and/or recovery.

Methods For Determining the Observed Color Restoration Benefit

The utility of a fabric color care active can be determined by thefollowing simple screening test procedures. The desired fabricproperties are determined using worn black chino (cotton) twill testfabric that is available from TESTFABRICS, Inc., West Pittston, Pa. Wornblack cotton twill test fabric is obtained by treating new fabricthrough eight treatment cycles, each washing/drying treatment cyclecomprises of one washing/rinsing cycle with the AATCC powder detergent,followed by two washing/rinsing cycles with clear water (withoutdetergent), all cycles using 90° C. water in a Kenmore automatic clotheswasher Model 110, followed by a drying cycle in a Kenmore automaticelectric tumble dryer Model 110. The resulting test fabric is visiblyworn and faded. Some worn fabric samples are retained for use as controlworn fabrics. Other worn fabric samples are treated using the method ofthe present invention. The control and treated fabrics are examinedvisually and their properties are determined by the following three testprocedures.

Reflectance

The reduction of reflectance of a fabric is determined using the opticalmeasurement from the LabScan®XE instrument from Hunter AssociatesLaboratory, Inc, Reston, Va. The LabScan®XE is a full-scanningspectrophotometer with a wavelength range from 400 to 700 nanometer. Thesample is illuminated by a xenon flash lamp and reflected light iscollected by a 15-station fiber optic ring. For reflectancemeasurements, the diameter of opening in port is 50 mm. The illuminationangle is 0° (normal) to the specimen. The viewing angle is 45° fromnormal via fiber optic ring.

The reflectance of the whole range of wavelength from about 420 nm toabout 620 nm is measured for the black cotton twill test fabrics. Foreach wavelength in an increment of about 10 nm, the reflectance of thetreated fabric (Rt) and that of the worn, untreated fabric (Ru) aremeasured. The percentage reduction of the reflectance for eachwavelength isΔR=100×{(ΣRu-ΣRt)/ΣRu}%

For a noticeable improvement and/or restoration of fabric color, ΔRshould be a positive number and having a value of at least about 3%,preferably at least about 5%, more preferably at least about 8%, andeven more preferably at least about 10%.

Hunter L Value

The rejuvenation/restoration of color of the worn/faded color fabric isfound to correlate with a reduction in the Hunter L value as definedbelow. The reduction of the Hunter L value of a fabric is determined byalso using the LabScan®XE instrument from the Hunter AssociatesLaboratory, Inc. According to its manual, the 0°/45° geometry of thisinstrument ‘sees’ the color the way the human eye sees color, itscircumferential viewing reduces the effect of sample directionality bydetecting light evenly from the entire measured surface, and itsspecular excluded mode measures the entire appearance of samples,including the color component and the geometric component (gloss andtexture). In a cylindrical space all color sensations can be arrangedaccording to the attributes lightness, hue, and chroma. Lightness (the Lvalue) is an attribute having end points white (L value of 100) andblack (L value of 0) and a continuous scale of greys between them. Theinternationally agreed upon system (Commission Internationale deI'Eclairage, CIE Publication No. 15, E-1.3.1, 1971) for convertinginstrument data into color data is the CIE system. The CIELAB formulaand its associated color space are based on a coordinate system withcoordinates L* for lightness, a* for redness-greenness and b* foryellowness-blueness.

Unlike normal color measurement, where all three values “L”, “a” and “b”are measured, in the determination of the color restoration benefit ofthe current invention, only the “L” values are determined, without aconsideration of the “a” and “b” values. The L values for the treatedblack cotton twill fabric, Lt, and that of the worn, untreated blackcotton twill fabric, Lu, are measured. The reduction of the L valueΔL=Lu−Ltshould be a positive number, and for an appreciable improvement ofcolor, ΔL should have a value of at least about 0.5, preferably at leastabout 1.0, more preferably at least about 1.5.Microfibril Number

An image analysis system is used to estimate the number of pills on theuntreated and treated black cotton twill fabrics that are used to definethe observed color restoration benefit. The general setup and procedureare described in “Efforts to Control Pilling in Wool/Cotton Fabrics”,Jeanette M. Cardamone, Textile Chemist and Colorist, 31, 27-31 (1999),incorporated herein by reference. The image analysis system that we usedutilizes a light booth with a circular fluorescent light bulb. The bulbis just above the plane of the fabric. The fabric is put into the lightbooth via a drawer. To remove any wrinkle the fabric is held down at theedges by a Plexiglas clamp (imagine a Plexiglas book with a hole in thecover where the fabric shows through). The pills rise above the fabricand reflect light to the monochrome camera, which is mounted above. Thecamera and video frame grabber are adjusted so that the pills show up asbright, and the plane of the fabric shows up as dark. Then the image isthresholded, and the bright blobs (pills) are counted and sized. Theimage analysis is done using a custom macro written in the OPTIMAS imageanalysis software package, available at the Meyer Instruments, Inc.,Houston, Tex. The “pill number ” (Pt) for the treated black cotton twillfabric and that of the worn, untreated fabric (Pt) are determined. Thepercentage reduction of the pill number ΔP isΔP=100×(Pu−Pt)/Pu%

It is found that for an appreciable color restoration benefit providedby a fabric color care composition, ΔP should be a positive number andhaving a value of at least about 10%, preferably at least by about 20%,more preferably at least about 40%, and even more preferably at leastabout 80%.

It is highly desirable to use actives that provide other benefits suchas reduction of wrinkles, maintenance of garment shape, soil release,etc., since the process used herein requires substantially completetreatment of the visible portions of the fabric with relatively highlevels of active and a consumer will normally be reluctant to invest thetime, money, and effort required to make sure that all areas areproperly covered. It is known that the color restoration benefit can beachieved by use of rinse-added and dryer-added fabric softeners astaught by the applicants herein. However, the total of active requiredin the rinse is much greater since the active is applied to the fabricin depth, and even with the best dryer-added fabric softeners that arerelease from a carrier such as a flexible substrate, the distributioncan be less than perfect the first time.

A preferred fabric color care active of the present invention comprisesof water dispersible, preferably water soluble polymers. They can benatural, or synthetic polymers and can act by forming a film, and/or byproviding adhesive properties. E.g., the present invention canoptionally use film-forming and/or adhesive polymer to also impart shaperetention to fabric, particularly clothing. By “adhesive” it is meantthat when applied as a solution or a dispersion to a fiber surface anddried, the polymer can attach to the surface. The polymer can form afilm on the surface, or when residing between two fibers and in contactwith the two fibers, it can bond the two fibers together.

Natural Polymers

A preferred fabric color care active of the present invention includewater soluble and/or water dispersible natural polymers which arederived from natural sources, preferably polysaccharides,oligosaccharides, proteins; substituted versions of said polymers;derivatised versions of said polymers; and mixtures thereof. Thepreferred polymer is colorless, to minimize the change of hue and toimprove the color fidelity.

A preferred active is selected from the group consisting ofpolysaccharides; proteins; glycoproteins; glycolipids; substitutedversions of said polymers; derivatised versions of said polymers; andmixtures thereof.

Synthetic Polymers

Another preferred fabric color care active of the present inventioninclude water soluble and/or water dispersible synthetic polymers. Thepreferred polymer is colorless, to minimize the change of hue and toimprove the color fidelity. Fabric color care synthetic polymerincludes: homopolymer and copolymer containing hydrophilic monomersand/or hydrophobic monomers.

Another preferred fabric color care synthetic polymer includes:dimethylsiloxane silicones and their derivatives. A class of siliconederivatives that is also preferred in the present invention is siliconecopolyols.

Surfactant Capable of Forming a Bilayer Structure

Surfactants capable of forming a bilayer structure are those that canform a vesicle or liposome. Surfactant capable of forming a bilayerstructure is useful fabric color care active in the spray composition ofthe present invention. Said surfactant comprises natural and syntheticmaterials. An example of natural surfactant include the phospholipids.Nonlimiting examples of synthetic surfactants include fabric softeningactives and sorbitan esters of long chain (C₁₆-C₁₈) fatty acids.

A preferred fabric color care composition for treating worn and/or fadedfabric comprises an effective amount of said fabric color care active,and optionally, at least one adjunct ingredients selected from the groupconsisting of: perfume, odor control agent including cyclodextrin,antimicrobial active and/or preservative, surfactant, opticalbrightener, antioxidant, chelating agent including aminocarboxylatechelating agent, antistatic agent, dye transfer inhibiting agent, fabricsoftening active, static control agent, or mixtures thereof.

Cationic dye fixing agents are not preferred in the composition of thepresent invention, because these materials are based on quaternizednitrogen compound or on nitrogen compounds having a strong cationiccharge which is formed in situ under the conditions of usage. Thesematerials are often substantive to the fabric and attract the fugitivedyes in the subsequent wash and rinse cycles, and can discolor and/orchange the color and/or hue of the treated color fabric. Enzymes arealso not preferred in the composition of the present invention,specially in the spray compositions, because aerosolized particlescontaining enzymes often constitute a health hazard.

The composition is typically applied to fabric via a positive step,e.g., spraying, dipping, soaking and/or padding process to treatsubstantially all of the visible surface followed by a drying step,including the process comprising a step of treating or spraying thefabric with the fabric care composition either outside or inside anautomatic clothes dryer followed by, or concurrently with, the dryingstep in said clothes dryer. The application can be done industrially bylarge scale processes on textiles and/or finished garments and clothing,or, preferably, in the consumer's home by the use of commercial product.

The fabric color care spray composition contains fabric color careactive at a level of from about 0.01% to about 20%, typically from about0.05% to about 10%, preferably from about 0.1% to about 5%, morepreferably from about 0.2% to about 3%, even more preferably from about0.3% to about 2%, by weight of the usage composition.

The present invention also relates to concentrated liquid or solidfabric color care compositions, which are diluted to form compositionswith the usage concentrations, as given hereinabove, for use in the“usage conditions”. Concentrated compositions comprise a higher level offabric color care active, typically from about 1% to about 99%,preferably from about 2% to about 65%, more preferably from about 3% toabout 25%, by weight of the concentrated fabric color care composition.Concentrated compositions are used in order to provide a less expensiveproduct per use. When a concentrated produce is used, i.e., when thefabric color care active is from about 1% to about 99%, by weight of theconcentrated composition, it is preferably to dilute the compositionbefore treating fabric. Preferably, the concentrated fabric care isdiluted with about 50% to about 10,000%, more preferably from about 50%to about 8,000%, and even more preferably from about 50% to about5,000%, by weight of the composition, of water.

The present invention preferably comprises articles of manufacture thatuse such fabric color care compositions. Thus the present inventionrelates to the compositions incorporated into a spray dispenser tocreate an article of manufacture that can facilitate treatment of fabricsurfaces with said fabric care compositions containing a fabric colorcare active and other optional ingredients at a level that is effective,yet is not discernible when dried on the surfaces. The spray dispensercomprises manually activated and non-manual powered (operated) spraymeans and a container containing the fabric color care composition. Fora non-manually operated sprayer, preferably battery powered for safetyreasons in the home, the container is preferably the one sold in thestore containing the fabric color care composition that is applied tothe fabric, adapted to be used with the particular sprayer. Theinvention also comprises containers that are adapted for use with spraydispensers.

Preferably the articles of manufacture are in association with a set ofinstructions for how to use the composition to treat fabric correctly,to obtain the desirable fabric care results, color renewal, and,preferably, other additional fabric care benefits, such as wrinkleremoval, wrinkle resistance, fiber strengthening/anti-water, pillprevention, anti-shrinkage, soiling prevention and/or reduction, and/orfabric shape retention, including, e.g., the manner and/or amount ofcomposition to used, and the preferred ways of checking for completenessof application, stretching and/or smoothing of the fabrics. Ironingand/or smoothing can help distribute the active over the surface andpartially compensate for incomplete distribution. As used herein, thephrase “in association with” means the instructions are either directlyprinted on the container itself or presented in a different mannerincluding, but not limited to, a brochure, print advertisement,electronic advertisement, and/or verbal communication, so as tocommunicate the set of instructions to a consumer of the article ofmanufacture. It is important that the instructions be as simple andclear as possible, so that using pictures and/or icons is desirable.

I. COMPOSITION

Fabric Color Care Active

The fabric color care spray composition contains fabric color careactive at a level of from about 0.01% to about 20%, typically from about0.05% to about 10%, preferably from about 0.1% to about 5%, morepreferably from about 0.2% to about 3%, even more preferably from about0.3% to about 2%,by weight of the usage composition.

The present invention also relates to concentrated liquid or solidfabric color care compositions, which are diluted to form compositionswith the usage concentrations, as given hereinabove, for use in the“usage conditions”. Concentrated compositions comprise a higher level offabric color care active, typically from about 1% to about 99%,preferably from about 2% to about 65%, more preferably from about 3% toabout 25%, by weight of the concentrated fabric color care composition.Concentrated compositions are used in order to provide a less expensiveproduce per use. When a concentrated produce is used, i.e., when thefabric color care active is from about 1% to about 99%, by weight of theconcentrated composition, it is preferable to dilute the compositionbefore treating fabric. Preferably, the concentrated fabric care isdiluted with about 50% to about 10,000%, more preferably from about 50%to about 8,000%, and even more preferably from about 50% to about5,000%, by weight of the composition, of water.

Typical rinse additive compositions contain a level of fabric color careactive of from 0.05% to about 50%, preferably from about 1% to about35%, more preferably from about 2% to about 18%, and even morepreferably from about 3% to about 10%, by weight of the rinse addedcompositions.

Preferred color care active includes polymers which can act by forming afilm, and/or by providing adhesive properties. By “adhesive” it is meantthat when applied as a solution or a dispersion to a fiber surface anddried, the polymer can attach to the surface. The polymer can form afilm on the surface, or when residing between two fibers and in contactwith the two fibers, it can bond the two fibers together. E.g., thepresent invention can use film-forming and/or adhesive polymer toprovide color restoration to worn, faded fabric. The present inventioncan optionally use film-forming and/or adhesive polymer to also impartshape retention to fabric, particularly clothing. Useful polymersinclude natural polymers, synthetic polymers, and mixtures thereof.These polymers are preferably colorless, to minimize the change of hueand to improve the color fidelity.

Water Soluble and Water Dispersible Natural Polymers

A fabric color care active useful in the present invention compriseswater soluble and/or water dispersible polymers derived from naturalsources, preferably selected from the group consisting ofpolysaccharides; proteins; glycoproteins; glycolipids; substitutedversions thereof; derviatised versions thereof; and mixtures thereof.

Preferably the fabric color care active is selected from the groupconsisting of polysaccharides and proteins. Preferably, saidpolysaccharides have a molecular weight of from about 1,000 to about2,000,000, more preferably from about 5,000 to about 1,000,000, and evenmore preferably from about 10,000 to about 300,000. Nonlimiting examplesof water soluble/dispersible polysaccharides useful in the presentinvention includes the following:

-   (i) Heteropolysaccharides derived from the bark, seeds, roots and    leaves of plants, which are divided into two distinct groups,    namely, acidic polysaccharides described as gums, mucilages and    pectins, and the neutral polysaccharides known as hemicelluloses,-   (ii) Algal polysaccharides including food-reserve polysaccharides    (e.g., laminaran), structural polysaccharides (e.g., D-xylans,    D-mannans), sulphated polysaccharides that are isolated from algae    (e.g., carregeenan, agar), other algal mucilages which have similar    properties and usually contain L-rhamnose, D-xylose, D-glucoronic    acid, D- and L-galactose and D-mannose,-   (iii) Microbial polysaccharides, such as teichoic acids, cell wall    peptidoglycans (mureins), extracellular polysaccharides,    gram-positive bacterial capsular polysaccharides and gram-negative    bacterial capsular polysaccharides.-   (iv) Lipopolysaccharides,-   (v) Fungal polysaccharides, and-   (vi) Animal polysaccharides (e.g., glycogen, chitin).

A preferred fabric color care polysaccharide is hemicellulose selectedfrom the group consisting of L-arabino-D-galactan; D-gluco-D-mannan,D-galacto-D-gluco-d-mannan, partly acetylated(4-O-methyl-D-glucuron)-D-xylan,L-arabino-(4-O-methyl-D-glucurono-)-D-xylan; substituted versionsthereof; derivatised versions thereof; and mixtures thereof; and morepreferably, arabinogalactan. Arabinogalactans are long, densely branchedhigh-molecular weight polysaccharides. Arabinogalactan that is useful inthe composition of the present invention has a molecular weight range offrom about 5,000 to about 500,000, preferably from about 6,000 to about250,000, more preferably from about 10,000 to about 150,000. Thesepolysaccharides are highly branched, consisting of a galactan backbonewith side-chains of galactose and arabinose units. Most commercialarabinogalactan is produced from western larch, through acounter-current extraction process. Larch arabinogalactan is watersoluble and is composed of arabinose and galactose units in about a 1:6ratio, with a trace of uronic acid. The molecular weights of thepreferred fractions of larch arabinogalactan include one fraction in therange of from about 14,000 to about 22,000, mainly from about 16,000 toabout 21,000, and the other in the range of from about 60,000 to about500,000mainly from about 80,000 to about 120,000. The fraction that hasthe average molecular weight of from about 16,000 to about 20,000 ishighly preferred for use in direct applications to fabric, such as inspray-on products.

Cationic polysaccharides such as chitins are also useful in the presentinvention. Chitin, a linear polysaccharide consisting ofN-acetyl-D-glucosamine, is widely distributed in nature, e.g., in theshells of crustaceans and insects, and in the cell wall of bacteria.Chemically, chitin is very similar to cellulose, differing only in thefact that chitin has an aminoacetyl group instead of hydroxyl group atC-2. Inspite of the similarity in structure with cellulose, the chemicaland physical properties of chitin are significantly different from thoseof cellulose.

Water Soluble/Dispersible Proteins

Nonlimiting examples of water soluble/dispersible proteins useful in thepresent invention includes: globular proteins, such as albumins,globulins, protamines, histones, prolamines and glutelins; low levels offibrous proteins, such as elastin, fibroin and sericin; and conjugatedproteins with one or more non-protein moieties such as carbohydrates,lipids, and phosphate residues. The proteins useful herein preferably donot include enzymes, specially in the spray compositions, becauseaerosolized particles containing enzymes often constitute a healthhazard.

Water Soluble and Water Dispersible Synthetic Polymers

Water soluble and water dispersible synthetic polymers useful in thepresent invention are comprise of monomers. Some nonlimiting examples ofmonomers which can be used to form the synthetic polymers of the presentinvention include: low molecular weight C₁-C₆ unsaturated organicmono-carboxylic and polycarboxylic acids, such as acrylic acid,methacrylic acid, crotonic acid, maleic acid and its half esters,itaconic acid, and mixtures thereof; esters of said acids with C₁-C₁₂alcohols, such as methanol, ethanol, 1-propanol, 2-propanol, 1-butanol,2-methyl-1-propanol, 1-pentanol, 2-pentanol, 3-pentanol,2-methyl-1-butanol, 1-methyl-1-butanol, 3-methyl-1-butanol,1-methyl-1-pentanol, 2-methyl-1-pentanol, 3-methyl-1-pentanol,t-butanol, cyclohexanol, 2-ethyl-1-butanol, neodecanol, 3-heptanol,benzyl alcohol, 2-octanol, 6-methyl-1-heptanol, 2-ethyl-1-hexanol,3,5-dimethyl-1-hexanol, 3,5,5-trimethyl-1-hexanol, 1-decanol,1-dodecanol, and the like, and mixtures thereof. Nonlimiting examples ofsaid esters are methyl acrylate, ethyl acrylate, t-butyl acrylate,methyl methacrylate, hydroxyethyl methacrylate, methoxy ethylmethacrylate, and mixtures thereof; amides and imides of said acids,such as N,N-dimethylacrylamide, N-t-butyl acrylamide, maleimides; lowmolecular weight unsaturated alcohols such as vinyl alcohol (produced bythe hydrolysis of vinyl acetate after polymerization), allyl alcohol;esters of said alcohols with low molecular weight carboxylic acids, suchas, vinyl acetate, vinyl propionate; ethers of said alcohols such asmethyl vinyl ether; aromatic vinyl such as styrene, alpha-methylstyrene,t-butylstyrene, vinyl toluene, polystyrene macromer, and the like; polarvinyl heterocyclics, such as vinyl pyrrolidone, vinyl caprolactam, vinylpyridine, vinyl imidazole, and mixtures thereof; other unsaturatedamines and amides, such as vinyl amine, diethylene triamine,dimethylaminoethyl methacrylate, ethenyl formamide; vinyl sulfonate;salts of acids and amines listed above; low molecular weight unsaturatedhydrocarbons and derivatives such as ethylene, propylene, butadiene,cyclohexadiene, vinyl chloride; vinylidene chloride; and mixturesthereof and alkyl quaternized derivatives thereof, and mixtures thereof.Preferably, said monomers are selected from the group consisting ofvinyl alcohol; acrylic acid; methacrylic acid; methyl acrylate; ethylacrylate; methyl methacrylate; t-butyl acrylate; t-butyl methacrylate;n-butyl acrylate; n-butyl methacrylate; isobutyl methacrylate;2-ethylhexyl methacrylate; dimethylaminoethyl methacrylate; N,N-dimethylacrylamide; N,N-dimethyl methacrylamide; N-t-butyl acrylamide;vinylpyrrolidone; vinyl pyridine; adipic acid; diethylenetriamine, saltsthereof and alkyl quaternized derivatives thereof, and mixtures thereof.

Preferably, said monomers form homopolymers and/or copolymers that arewater soluble or dispersible in water and have a molecular weight of atleast about 500, preferably from about 1,000 to about 2,000,000, morepreferably from about 4,000 to about 1,000,000, and even more preferablyfrom about 10,000 to about 300,000 for some polymers.

Polymers useful in the present invention can comprise homopolymers andcopolymers of hydrophilic monomers and hydrophobic monomers. Thecopolymer can be linear random or block copolymers, and mixturesthereof. The hydrophobic/hydrophilic copolymers typically have ahydrophobic monomer/hydrophilic monomer ratio of from about 5:95 toabout 95:5, preferably from about 15:85 to about 85:15, more preferablyfrom about 30:70 to about 75:25, by weight of the copolymer. Thehydrophobic monomer can comprise a single hydrophobic monomer or amixture of hydrophobic monomers, and the hydrophilic monomer cancomprise a single hydrophilic monomer or a mixture of hydrophilicmonomers. The term “hydrophobic” is used herein consistent with itsstandard meaning of lacking affinity for water, whereas “hydrophilic” isused herein consistent with its standard meaning of having affinity forwater. As used herein in relation to monomer units and polymericmaterials, including the copolymers, “hydrophobic” means substantiallywater insoluble; “hydrophilic” means substantially water soluble. Inthis regard, “substantially water insoluble” shall refer to a materialthat is not soluble in distilled (or equivalent) water, at 25° C., at aconcentration of about 0.2% by weight, and preferably not soluble atabout 0.1% by weight (calculated on a water plus monomer or polymerweight basis). “Substantially water soluble” shall refer to a materialthat is soluble in distilled (or equivalent) water, at 25° C., at aconcentration of about 0.2% by weight, and are preferably soluble atabout 1% by weight. The terms “soluble”, “solubility” and the like, forpurposes hereof, corresponds to the maximum concentration of monomer orpolymer, as applicable, that can dissolve in water or other solvents toform a homogeneous solution, as is well understood to those skilled inthe art.

Nonlimiting examples of useful hydrophilic monomers are unsaturatedorganic mono-carboxylic and polycarboxylic acids, such as acrylic acid,methacrylic acid, crotonic acid, maleic acid and its half esters,itaconic acid; unsaturated alcohols, such as vinyl alcohol, allylalcohol; polar vinyl heterocyclics, such as vinyl pyrrolidone, vinylcaprolactam, vinyl pyridine, vinyl imidazole; vinyl amine; vinylsulfonate; unsaturated amides, such as acrylamides, e.g.,N,N-dimethylacrylamide, N-t-butyl acrylamide; hydroxyethyl methacrylate;dimethylaminoethyl methacrylate; salts of acids and amines listed above,and the like; and mixtures thereof. Some preferred hydrophilic monomersare acylic acid, methacrylic acid, N,N-dimethyl acrylamide, N,N-dimethylmethacrylamide, N-t-butyl acrylamide, dimethylamino ethyl methacrylate,vinyl pyrrolidone, salts thereof and alkyl quaternized derivativesthereof, and mixtures thereof.

Nonlimiting examples of useful hydrophobic monomers are acrylic acidC₁-C₁₈ alkyl esters, such as methyl acrylate, ethyl acrylate, t-butylacrylate; methacrylic C₁-C₁₈ alkyl esters, such as methyl methacrylate,2-ethyl hexyl methacrylate, methoxy ethyl methacrylate; vinyl alcoholesters of carboxylic acids, such as, vinyl acetate, vinyl propionate,vinyl neodecanoate; aromatic vinyls, such as styrene, t-butyl styrene,vinyl toluene; vinyl ethers, such as methyl vinyl ether; vinyl chloride;vinylidene chloride; ethylene, propylene and other unsaturatedhydrocarbons; and the like; and mixtures thereof. Some preferredhydrophobic monomers are methyl acrylate, methyl methacrylate, t-butylacrylate, t-butyl methacrylate, n-butyl acrylate, n-butyl methacrylate,and mixtures thereof.

Some non-limiting examples of water soluble and water dispersiblehomopolymers include polyacrylic acid, polyacrylamide; polymethacrylicacid; polymethacrylamide; polyvinyl alcohol; polyvinyl acetate;polyvinylpyrrolidone; polyvinyloxazolidone; polyvinylmethyloxazolidone;polyethylene oxide; polypropylene oxide; polyvinylpyridine n-oxide;polyquaternary amine resins; poly(ethenylformaide); poly(vinylamine)hydrochloride; and mixtures thereof. Many of these polymers aredescribed with more details in “Water-Soluble Synthetic Polymers:Properties and Behavior, Volum I, Philip Molyneux, published by CRCPress, 1983, incorporated herein by reference. Preferably saidhomopolymers are selected from the group consisting of polyvinylalcohol; polyvinyl acetate; polyacrylic acid; polyacrylamide;polymethacrylic acid; polymethacrylamide; polyvinylpyrrolidone;polyvinyloxazolidone; polyethylene oxide; polypropylene oxide;polyvinylpyridine n-oxide; and mixtures thereof.

Some non-limiting examples of copolymers which can be used as fabriccolor care active of the present invention are: adipicacid/dimethylaminohydroxypropyl diethylenetriamine copolymer; adipicacid/epoxypropyl diethylenetriamine copolymer;poly(vinylpyrrolidone/dimethylaminoethyl methacrylate); methacryloylethyl betaine/methacrylates copolymer; ethyl acrylate/methylmethacrylate/methacrylic acid/acrylic acid copolymer; poly(vinylalcohol-co-6% vinylamine); poly(vinyl alcohol-co-12% vinylamine);poly(vinyl alcohol-co-6% vinylamine hydrochloride); and poly(vinylalcohol-co-12% vinylamine hydrochloride). Preferably, said copolymer areselected from the group consisting of adipicacid/dimethylaminohydroxypropyl diethylenetriamine copolymer;poly(vinylpyrrolidone/dimethylaminoethyl methacrylate); ethylacrylate/methyl methacrylate/methacrylic acid/acrylic acid copolymer;methacryloyl ethyl betaine/methacrylates copolymer; polyquaternary amineresins; poly(ethenylformamide); poly(vinylamine) hydrochloride;poly(vinyl alcohol-co-6% vinylamine); poly(vinyl alcohol-co-12%vinylamine); poly(vinyl alcohol-co-6% vinylamine hydrochloride); andpoly(vinyl alcohol-co-12% vinylamine hydrochloride).

Nonlimiting examples of the preferred polymer that are commerciallyavailabe are: polyvinylpyrrolidone/dimethylaminoethyl methacrylatecopolymer, such as Copolymer 958®, molecular weight of about 100,000 andCopolymer 937, molecular weight of about 1,000,000, available from GAFChemicals Corporation, adipic acid/dimethylaminohydroxypropyldiethylenetriamine copolymer, such as Cartaretin F-4® and F-23,available from Sandoz Chemicals Corporation; methacryloyl ethylbetaine/methacrylates copolymer, such as Diaformer Z-SM®, available fromMitsubishi Chemicals Corporation; polyvinyl alcohol copolymer resin,such as Vinex 2019®, available from Air Products and Chemicals orMoweol®, available from Clariant; adipic acid/epoxypropyldiethylenetriamine copolymer, such as Delsette 101®, available fromHercules Incorporated; and polyvinylpyrrolidone/acrylic acid, such asSokalan EG 310®, available from BASF.

Non limiting examples of polymers for use in the present inventioninclude the following, where the composition of the copolymer is givenas approximate weight percentage of each monomer used in thepolymerization reaction used to prepare the polymer: vinylpyrrolidone/vinyl acetate copolymers (at ratios of up to about 30% byweight of vinyl pyrrolidone); dimethyl acrylamide/ t-butylacrylate/ethyl hexyl methacrylate copolymer (10/45/45); vinylpyrrolidone/vinyl acetate/butyl acrylate copolymer (10/78/12 and10/70/20); vinyl pyrrolidone/vinyl propionate copolymer (5/95); vinylcaprolactam/vinyl acetate copolymer (5/95); acrylic acid/t-butylacrylate (25/75) and styling resins sold under the trade names UltraholdCA 8® by Ciba Geigy (ethyl acrylate/acrylic acid/N-t-butyl acrylamidecopolymer); Resyn 28-1310® by National Starch and Luviset CA 66® by BASF(vinyl acetate/crotonic acid copolymer 90/10); Luviset Cap® by BASF(vinyl acetate/vinyl propionate/crotonic acid 50/40/10); Resyn 28-2930®by National Starch (vinyl acetate/vinyl neodecanoate/crotonic acidcopolymer), Amerhold DR-25® by Union Carbide (ethyl acrylate/methacrylicacid/methyl methyacrylate/acrylic acid copolymer), and Poligen A® byBASF (polyacrylate dispersion).

A preferred fabric color care active comprises copolymers containhydrophobic monomers and hydrophilic monomers which comprise unsaturatedorganic monocarboxylic and polycarboxylic acid monomers, such as acrylicacid, methyacrylic acid, crotonic acid, maleic acid and its half esters,itaconic acid, and salts thereof, and mixtures thereof; and optionallyother hydrophilic monomers. Examples of the hydrophilic unsaturatedorganic mono-carboxylic and polycarboxylic acid monomers are acrylicacid, methyacrylic acid, crotonic acid, maleic acid and its half esters,itaconic acid, and mixtures thereof. Nonlimiting examples of thehydrophobic monomers are esters of the unsaturated organicmono-carboxylic and polycarboxylic acids cited hereinabove with C₁-C₁₂alcohols, such as methanol, ethanol, 1-proponal, 2-proponal, 1-butanol,2-methyl-1-proponal, 1-pentanol, 2-pentanol, 3-pentanol,2-methyl-1-butanol, 1-methyl-1-butanol, 3-methyl-1-butanol,1-methyl-1-pentanol, 2-methyl-1-pentanol, 3-methyl-1-pentanol,1-butanol, cyclohexanol, 2-ethyl-1-butanol, and mixtures thereof,preferably methanol, ethanol, 1-propanol, 2-propanol, 1-butanol,2-methyl-1-propanol, t-butanol, and mixtures thereof. One preferredcopolymer contains acrylic acid and t-butyl acrylate monomeric units,preferably with acrylic acid/t-butyl acrylate ratios from about 90:10 toabout 10:90, preferably from about 70:30 to about 15:85, more preferablyfrom about 40:60 to about 20:80. Nonlimiting examples of acrylicacid/tert-butyl acrylate copolymers useful in the present invention arethose typically with a molecular weight of from about 1,000 to about2,000,000, preferably from about 5,000 to about 1,000,000, and morepreferably from about 30,000 to about 300,000, and with an approximateacrylic acid/tert-butyl acrylate weight ratio of about 25:75 and anaverage molecular weight of from about 70,000 to about 100,000, andthose with an approximate acrylic acid/tert-butyl acrylate weight ratioof about 35:65 and an average molecular weight of from about 60,000 toabout 90,000.

A class of water-soluble polymers containing nitrogen and oxygen atomsuseful in the present invention for fabric colorrestoration/rejuvenation can also be used as dye transfer inhibitingagents. These polymers have the ability to complex or absorb thefugitive dyes washed out of dyed fabrics before the dyes have theopportunity to become attached to other articles in the wash or therinse. Nonlimiting examples of these actives are polyvinylpyrrolidonepolymers, poly(4-vinylpyridine-N-oxide), polyamine N-oxide polymers,copolymers of N-vinylpyrrolidone and N-vinylimidazole,polyvinyloxazolidones and polyvinylimidazoles or mixtures thereof.Examples of such dye transfer inhibiting agents are disclosed in U.S.Pat. No. 5,804,219, issued Sep. 8, 1998 to T. Trinh, S. L.-L. Sung, H.B. Tordil, and P. A. Wendland, and in U.S. Pat. Nos. 5,707,950 and5,707,951, all are incorporated herein by reference.

Polyalkyleneterephthlate Copolymers

Another fabric color care active suitable in the present inventioncomprises block copolymers of polyalkylene terephthalate andpolyoxyethylene terephthalate, and block copolymers of polyalkyleneterephthalate and polyethylene glycol. The polyalkylene terephthalateblocks preferably comprise ethylene and/or propylene groups. Many suchpolymers are nonionic.

A preferred nonionic polymer has the following average structure:CH₃O(CH₂CH₂O)₄₀ —[C(O)—C₆H₄—C(O)—OCH₂CH(CH₃)O—]₅—C(O)—C₆H₄—C(O)—(OCH₂CH₂—)₄₀OCH₃.

Such polymers are described in U.S. Pat. No. 4,849,257, Borcher, Trinhand Bolich, issued Jul. 18, 1989. Another preferred nonionic polymer isdescribed in New Zealand Pat. No. 242,150, issued Aug. 7, 1995 to Pan,Gosselink, and Honsa, said patents are incorporated herein by reference.

Other suitable polymers that are useful in the present inventioncomprise anionic and cationic polymers. Suitable anionic polymers oroligomers are disclosed in U.S. Pat. No. 4,018,569, Trinh, Gosselink andRattinger, issued Apr. 4, 1989. Suitable cationic polymers are describedin U.S. Pat. No. 4,956,447, Gosselink, Hardy, and Trinh, issued Sep. 11,1990. Other suitable polymers are disclosed in U.S. Pat. No. 4,808,086,Evans, Huntington, Stewart, Wolf, and Zimmerer, issued Feb. 24, 1989.All said patents are incorporated herein by reference.

The above polyalkylene terephthalate copolymers can be used in thecomposition of the present invention to additionally provide a soilrelease benefit.

Silicones

Another preferred fabric color care active comprises silicones and theirderivatives. Nonlimiting examples of useful silicones in the compositionof the present invention include noncurable silicones such aspolydimethylsilicone, and curable silicones such as aminosilicones,phenylsilicones and hydroxysilicones. The word “silicone” are usedherein preferably refers to emulsified silicones, including those thatare commercially available and those that are emulsified in thecomposition, unless otherwise described.

The silicones that are preferred in the composition of the presentinvention is polyalkyl and/or phenylsilicones silicone fluids and gumswith the following structure:A—Si(R₂)—O—[Si(R₂)—O—]_(q)—Si(R₂)—A

The alkyl groups substituted on the siloxane chain (R) or at the ends ofthe siloxane chains (A) can have any structure as long as the resultingsilicones remain fluid at room temperature.

Each R group preferably can be alkyl, aryl, hydroxy, or hydroxyalkylgroup, and mixtures thereof, more preferably, each R is methyl, ethyl,propyl or phenyl group, most preferably R is methyl. Each A group whichblocks the ends of the silicone chain can be hydrogen, methyl, methoxy,ethoxy, hydroxy, propoxy, and aryloxy group, preferably methyl. SuitableA groups include hydrogen, methyl, methoxy, ethoxy, hydroxy, andpropoxy. q is preferably an integer from about 7 to about 8,000. Thepreferred silicones are polydimethyl siloxanes; more preferred siliconesare polydimethyl siloxanes having a viscosity of from about 50 to about5,000 centistrokes at 25° C. Suitable examples include silicones offeredby Dow Corning Corporation and General Electric Company.

Other useful silicone materials, but less preferred than polydimethylsiloxanes, include materials of the formula:HO—[Si(CH₃)₂—O]_(x)—{Si(OH)[(CH₂)₃—NH—(CH₂)₂—NH₂]O}_(y)—Hwherein x and y are integers which depend on the molecular weight of thesilicone, preferably having a viscosity of from about 10,000 cst toabout 500,000 cst at 25° C. This material is also known as“amodimethicone”. These aminofunctional silicones are highly substantiveto fabrics.

When the composition of this invention is to be dispensed from a spraydispenser in a consumer household setting, the noncurable silicones suchas polydimethylsilicone, are preferred. Curable and/or reactivesilicones such as aminofunctional silicones and silicones with reactivegroups such as Si—OH, Si—H, silanes, and the like, are not preferred inthis situation, because the portion of the composition that is sprayedbut misses the garment, and falls instead on flooring surfaces, such asrung, carpet, concrete floor, tiled floor, linoleum floor, bathtubfloor, can leave a silicone layer that is cured and/or bonded to theflooring surfaces. Such silicones that are bonded to surfaces aredifficult to be removed from the flooring surfaces. Flooring surfacesthus become slippery and can present a safety hazard to the householdmembers. The curable and reactive silicones can be used in compositionsspecifically designed for use in enclosed areas such as in a dewrinklingcabinet. Many types of aminofunctional silicones also cause fabricyellowing. Thus, the silicones that cause fabric discoloration are alsonot preferred.

Another silicone material which can be used, but is less preferred thanpolydimethyl siloxanes, has the formula:(CH₃)₃Si—[O—Si(CH₃)₂]_(n)—{OSi(CH₃)[(CH₂)₃—NH—(CH₂)₂—NH₂]}_(m)—OSi(CH₃)₃wherein the sum of n+m is a number from 2 to about 1,000. The preferredsilicones of this type are those which do not cause fabricdiscoloration.

The fabric color care silicones can also impart a lubricating property,and are useful in the composition to provide fabric wrinkle controlbenefit.

A preferred class of silicone derivatives that are useful in the presentinvention are the silicone copolyols. Nonlimiting examples of siliconecopolyols are the polyalkylene oxide polysiloxanes having a dimethylpolysiloxane hydrophobic moiety and one or more hydrophilic polyalkyleneside chains, and having the general formula:R¹—(CH₃)₂SiO—[(CH₃)₂SiO]_(a)—[(CH₃)(R¹)SiO]_(b)—Si(CH₃)₂—R¹wherein a+b are from about 1 to about 50, preferably from about 3 toabout 30, more preferably from about 10 to about 25, and each R¹ is thesame or different and is selected from the group consisting of methyland a poly(ethyleneoxide/propyleneoxide) copolymer group having thegeneral formula:—(CH₂)_(n)O(C₂H₄O)_(c)(C₃H₆O)_(d)R²with at least one R¹ being a poly(ethyleneoxy/propyleneoxy) copolymergroup, and wherein n is 3 or 4, preferably 3; total c (for allpolyalkyleneoxy side groups) has a value of from 1 to about 100,preferably from about 6 to about 100; total d is from 0 to about 14,preferably from 0 to about 3; and more preferably d is 0; total c+d hasa value of from about 5 to about 150, preferably from about 9 to about100 and each R² is the same or different and is selected from the groupconsisting of hydrogen, an alkyl having 1 to 4 carbon atoms, and anacetyl group, preferably hydrogen and methyl group. Each polyalkyleneoxide polysiloxane has at least one R¹ group being apoly(ethyleneoxide/propyleneoxide) copolymer group.

Nonlimiting examples of this type of silicone copolyols are the Silwet®surfactants which are available from Witco Corporation. RepresentativeSilwet surfactants which contain only ethyleneoxy (C₂H₄O) groups are asfollows.

Name Average MW Average a + b Average total c L-7607 1,000 2 17 L-76056,000 20 99 L-7604 4,000 21 53 L-7600 4,000 11 68 L-7657 5,000 20 76L-7602 3,000 20 29 L-7622 10,000 88 75

Nonlimiting examples of surfactants which contain both ethyleneoxy(C₂H₄O) and propyleneoxy (C₃H₆O) groups are as follows.

Name Average MW EO/PO ratio Silwet L-720 12,000 50/50 Silwet L-700120,000 40/60 Silwet L-7002 8,000 50/50 Silwet L-7210 13,000 20/80 SilwetL-7200 19,000 75/25 Silwet L-7220 17,000 20/80

The molecular weight of the polyalkyleneoxy group (R¹) is less than orequal to about 10,000. Preferably, the molecular weight of thepolyalkyleneoxy group is less than or equal to about 8,000, and mostpreferably ranges from about 300 to about 5,000. Thus, the values of cand d can be those numbers which provide molecular weight within theseranges. However, the number of ethyleneoxy units (—C₂H₄O) in thepolyether chain (R¹) must be sufficient to render the polyalkylene oxidepolysiloxane water dispersible or water soluble. If propyleneoxy groupsare present in the polyalkylenoxy chain, they can be distributedrandomly in the chain or exist as blocks. Surfactants which contain onlypropyleneoxy groups without ethyleneoxy groups are less preferred.

Other useful silicone derivatives are those having a hydrophobic moietyand hydrophilic ionic groups, including, e.g., anionic, cationic, andamphoteric groups. Nonlimiting examples of anionic silicone surfactantsare silicone sulfosuccinates, silicone sulfates, silicone phosphates,silicone carboxylates, and mixtures thereof, as disclosed respectivelyin U.S. Pat. Nos. 4,717,498, 4,960,845, 5,149,765, and 5,296,434.Nonlimiting examples of cationic silicone surfactants are silicone alkylquats (quaternary ammoniums), silicone amido quats, silicone imidazolinequats, and mixtures thereof, as disclosed respectively in U.S. Pat. Nos.5,098,979, 5,135,294, and 5,196,499. Nonlimiting examples of amphotericsilicone surfactants are silicone betaines, silicone amino proprionates,silicone phosphobetaines, and mixtures thereof, as disclosedrespectively in U.S. Pat. Nos. 4,654,161, 5,073,619, and 5,237,035. Allof these patents are incorporated herein by reference.

A special type of synthetic fabric color care polymer useful in thepresent invention comprises graft and block copolymers of silicone withmoieties containing hydrophilic and/or hydrophobic monomers describedhereinbefore. The silicone-containing copolymers in the spraycomposition of the present invention provide color rejuvenation, and inaddition, other fabric care benefits such as shape retention body,and/or good, soft fabric feel. Preferred silicone-containing copolymerscontain hydrophobic monomers and hydrophilic monomers which compriseunsaturated organic mono-carboxylic and/or polycarboxylic acid monomers,such as acrylic acid, methacrylic acid, crotonic acid, maleic acid andits half esters, itaconic acid; and salts thereof; and mixtures thereof;and optionally other hydrophilic monomers.

Surfactant Capable of Forming a Bilayer Structure

Surfactants capable of forming a bilayer structure are those that canform a vesicle or liposome. Suitable surfactants include phospholipidssuch as phosphatidyl choline, phosphatidylethanolamine,phosphatidylinositol, lecithin, cephalin, plasmalogen and mixturesthereof, glycolipids such as cerbroside, sorbitan esters of long chain(C₁₆-C₁₈) fatty acids, lactic acid esters of long chain (C₁₆-C₁₈) fattyacid monoglycerides (e.g., Lactem), diacetyl tartaric acid esters oflong chain (C₁₆-C₁₈) fatty acid monoglycerides (e.g., Panodan FDPK), andmixtures thereof.

A preferred class of surfactants capable of forming a bilayer structureare the fabric softening actives. These materials are traditionally usedin rinse-added and dryer-added fabric softener compositions. In thecurrent invention, the fabric softening actives are preferably used infabric color care compositions that are applied directly to the worn,faded fabrics, such as by spraying, soaking, dipping, or padding,preferably spraying, which are very efficient. The treatment using saidfabric softening actives in the rinse for fabric color restorationbenefit is less efficient, and requires a high level of fabric softeningactive, and thus is less preferred. The method of using a dryer-addedfabric softener sheet in the dryer is also not preferred, because it canprovide a patchy, non-uniform coverage of the fabric visible surface,resulting in a poor fabric appearance.

Any fabric softening active, including quaternary and non-quaternarysoftening actives, with saturated, partially saturated, unsaturatedan/or highly unsaturated, with straight, linear alkyl chains and/orbranched alkyl groups, can be used in the fabric color care compositionof the present invention, to be applied directly to the worn, fadedfabric, preferably via a spraying mechanism. Biodegradable fabricsoftening actives are preferred.

A preferred fabric color care composition herein used fabric softeningactive with highly unsaturated and/or branched hydrophobic chains,preferably, biodegradable, selected from the highly unsaturated and/orbranched fabric softening actives, and mixtures thereof.

Preferred fabric softening actives of the invention comprise a majorityof compounds as follows:

Diester Quaternary Ammonium Fabric Softening Active Compound (DEQA)

(1) The first type of DEQA preferably comprises, as the principleactive, compounds of the formula{R_(4-m)—N⁺—[(CH₂)_(n)—Y—R¹]_(m)}A⁻wherein each R substituent is either hydrogen, a short chain C₁-C₆,preferably C₁-C₃ alkyl or hydroxyalkyl group, e.g., methyl (mostpreferred), ethyl, propyl, hydroxyethyl, and the like, poly (C₂₋₃alkoxy)preferably polyethoxy group, benzyl, or mixtures thereof; each m is 2 or3; each n is from 1 to about 4; each Y is —O—(O)C—, —C(O)—O—, —NR—C(O)—,or —C(O)—NR—; the sum of carbons in each R¹, plus one which Y is—O—(O)C— or —NR—C(O)—, is C₁₂-C₂₂, preferably C₁₄-C₂₀, with each R¹being a hydrocarbyl, or substituted hydrocarbyl group, and A⁻ can be anysoftener-compatible anion, preferably, chloride, bromide, methylsulfate,ethylsulfate, sulfate, and nitrate, more preferably chloride or methylsulfate. (As used herein, the “percent of softening active” containing agiven R¹ group is based upon taking a percentage of the total activebased upon the percentage that the given R¹ group is, of the total R¹groups present.)

(2) A second type of DEQA active has the general formula:[R₃N⁺CH₂CH(YR¹)(CH₂YR¹)]A⁻wherein each Y, R, R¹, and A⁻ have the same meaning as before. Suchcompounds include those having the formula:[CH₃]₃N⁽⁺⁾[CH₂CH(CH₂O(O)CR¹)O(O)CR¹]C1⁽⁻⁾where each R is a methyl or ethyl group and preferably each R¹ is in therange of C₁₅ to C₁₉.

These types of agents and general methods of making them are disclosedin U.S. Pat. No. 4,137,180, Naik et al., issued Jan. 30, 1979, which isincorporated herein by reference. An example of a preferred DEQA offormula (2) is the “propyl” ester quaternary ammonium fabric softeningactive having the formula 1,2-di(acyloxy)-3-trimethylammoniopropanechloride, where the acyl is the same as that of FA¹ mixture disclosedhereinafter.

These biodegradable quaternary ammonium fabric softening compoundspreferably contain the group C(O)R¹ which is preferably derived frompartially hydrogenated fatty acids from natural sources, e.g., derivedfrom animal fat, such as tallow fatty acids. More preferred areunsaturated fatty acids, e.g., oleic acid, and polyunsaturated fattyacids, such as those derived from vegetable oils, such as, canola oil,safflower oil, peanut oil, sunflower oil, corn oil, soybean oil, tailoil, rice bran oil, etc. Non-limiting examples of fatty acids (FA) arelisted in U.S. Pat. No. 5,759,990 at column 4, lines 45-66. Fabricsoftening actives containing unsaturated and polyunsaturated fatty acidsare preferred in formulating the fabric color care compositions of thepresent invention.

Iodine Value (referred to as “IV” herein) is used to define the level ofunsaturation of a fatty acid. As used herein, Iodine Value of the“parent” fatty acid, or “corresponding” fatty acid that the R¹ group isderived from, is also used to define the level of unsaturation of afabric softening active. The IV of the parent fatty acids of these R¹group is from about 0 to about 140, more preferably from about 40 toabout 130, on the average. For concentrate, clear compositions, The IVis preferably from about 70 to about 140, more preferably from about 80to about 130, and even more preferably from about 90 to about 115, onthe average.

It is preferred that at least a majority of the fatty acyl groups areunsaturated, e.g., from about 50% to 100%, preferably from about 55% toabout 100%, more preferably from about 60% to about 100%.

Another DEQA softening active that is suitable for the formulation ofthe fabric color care compositions of the present invention, has theabove formula (1) wherein one R group is a C₁₋₄ hydroxy alkyl group, orpolyalkoxy group, preferably hydroxy alkyl, more preferablyhydroxyethyl, group. An example of such a hydroxyethyl ester active isdi(acyloxyethyl)(2-hydroxyethyl)methyl ammonium methyl sulfate, wherethe acyl is derived from the fatty acids described hereinbefore, e.g.,oleic acid and other highly unsaturated fatty acids.

Polyquaternary Ammonium Softening Actives. Fabric softening activescarrying more than one positive quaternary ammonium charge are alsouseful in the fabric color care compositions of the present invention.An example of this type of softening active is that having the formula:

wherein each R is H or a short chain C₁-C₆, preferably C₁-C₃ alkyl orhydroxyalkyl group, e.g., methyl (most preferred), ethyl, propyl,hydroxyethyl, and the like, benzyl, or (R²O)₂₋₄H; each R¹ is a C₆-C₂₂,preferably C₁₄-C₂₀ hydrocarbyl, or substituted hydrocarbyl substituent,preferably C₁₀-C₂₀ alkyl or alkenyl (unsaturated alkyl, includingpolyunsaturated alkyl, also referred to sometimes as “alkylene”), mostpreferably C₁₂-C₁₈ alkyl or alkenyl; each R² is a C₁₋₆ alkylene group,preferably an ethylene group; and A⁻ are defined as below. Fabricsoftening actives having the following formula:

wherein R¹ is derived from oleic acid is available from Witco Company.

Softening active having the formula:R_(4-m)—N⁽⁺⁾—R¹ _(m) A⁻wherein each m is 2 or 3, each R¹ is a C₆-C₂₂, preferably C₁₄-C₂₀, butno more than one being less than about C₁₂ and then the other is atleast about 16, hydrocarbyl, or substituted hydrocarbyl substituent,preferably C₁₀-C₂₀ alkyl or alkenyl, most preferably C₁₂-C₁₈ alkyl oralkenyl, and where the Iodine Value of a fatty acid containing this R¹group is from 0 to about 140, more preferably from about 40 to about130; with a cis/trans ratio of from about 1:1 to about 50:1, the minimumbeing 1:1, preferably from about 2:1 to about 40:1, more preferably fromabout 3:1 to about 30:1, and even more preferably from about 4:1 toabout 20:1; each R¹ can also be a branched chain C₁₄-C₂₂ alkyl group,preferably a branched chain C₁₆-C₁₈ group; each R is H or a short chainC₁-C₆, preferably C₁-C₃ alkyl or hydroxyalkyl group, e.g., methyl (mostpreferred), ethyl, propyl, hydroxyethyl, and the like, benzyl, or(R²O)₂₋₄H; and A⁻ is a softening active compatible anion, preferably,chloride, bromide, methylsulfate, ethylsulfate, sulfate, and nitrate,more preferably chloride and methyl sulfate.

Other fabric softening actives that can be used herein are disclosed, atleast generically for the basic structures, in U.S. Pat. Nos.:3,408,361, Mannheimer, issued Oct. 29, 1968; 4,709,045; Kubo et al.,issued Nov. 24, 1987; 4,233,451, Pracht et al., issued Nov. 11, 1980;4,127,489, Pracht et al., issued Nov. 28, 1979; 3,689,424, Berg et al.,issued Sep. 5, 1972; 4,128,485, Baumann et al., issued Dec. 5, 1978;4,161,604, Elster et al., issued Jul. 17, 1979; 4,189,593, Wechsler etal., issued Feb. 19, 1980; 4,339,391, Hoffman et al., issued Jul. 13,1982 3,861,870, Edwards and Diehl; 4,308,151, Cambre; 3,886,075,Bernardino; 4,233,164, Davis; 4,401,578, Verbruggen; 3,974,076, Wiersemaand Rieke; 4,237,016, Rudkin, Clint, and Young, 4,885,102, Yamamura etal., issued Dec. 5, 1989; 4,937,008, Yamamura et al., issued Jun. 26,1990; and 5,133,885, Contor et al., issued Jul. 28, 1992; Case 4768C,Trinh et al.; and European patent applications 91/336,267, Rutzen et al.and 91/423,894, Contor et al. and International Patent WO 91/01295,Trius et al., published Feb. 7, 1991, all of said patients andapplications being incorporated herein by reference.

Other useful fabric softening actives are disclosed in U.S. Pat. No.4,661,269, issued Apr. 28, 1987, to T. Trinh, E. H. Wahl, D. M. Swartleyand R. L. Hemingway. Biodegradable ester and/or amide linked fabricsoftening actives are disclosed, e.g., in U.S. Pat. No. 5,545,340,issued Aug. 13, 1996, to Wahl et al. Biodegradable unsaturated esterand/or amide linked fabric softening actives in concentration clearcompositions are disclosed in U.S. Pat. No. 5,759,990, issued Jun. 2,1998 in the names of Wahl, Tordil, Trinh, Carr, Keys, and Meyer, and inU.S. Pat. No. 5,747,443, issued May 5, 1998 in the names of Wahl, Trinh,Gosselink, Letton, and Sivik. All said patents are incorporated hereinby reference.

Optional Ingredients

The fabric care composition of the present invention can optionallycontain surfactant, perfume, brightener, odor-controlling agent,antimicrobial active and/or preservative, antistatic agent, antioxidant,insect and moth repelling agent, and mixtures thereof. The total levelof optional ingredients is low, preferably less than about 5% morepreferably less than about 3%, and even more preferably less than about2%, by weight of the usage composition. These optional ingredientsexclude the other ingredients specifically mentioned hereinbefore.

Surfactant

Surfactant is an optional but highly preferred ingredient of the presentinvention. Surfactant is especially useful in the composition tofacilitate the dispersion and/or solubilization of color improvementagents such as silicones and/or perfumed. Such surfactant is preferablyincluded when the composition is used in a spray dispenser in order toenhance the spray characteristics of the composition and allow thecomposition, including the fabric color care active, to distribute moreevenly, and to prevent clogging of the spray apparatus. The spreading ofthe composition can also allow it to dry faster, so that the treatedmaterial is ready to use sooner. For concentrated compositions, thesurfactant facilitates the dispersion of many actives such asantimicrobial actives and perfumes in the concentrated aqueouscompositions. Suitable surfactant useful in the present invention isnonionic surfactant, anionic surfactant, cationic surfactant, amphotericsurfactant, and mixtures thereof.

When surfactant is used in the composition of the present invention, itis added at an effective amount to provide one, or more of the benefitsdescribed herein, typically from about 0.01% to about 5%, preferablyfrom about 0.05% to about 3%, more preferably from about 0.1% to about2%, and even more preferably, from about 0.2% to about 1%, by weight ofthe usage composition.

A preferred type of surfactant is ethoxylated surfactant, such asaddition products of ethylene oxide with fatty alcohols, fatty acids,fatty amines, etc. Optionally, addition products of mixtures of ethyleneoxide and propylene oxide with fatty alcohols, fatty acids, fatty aminescan be used. The ethoxylated surfactant includes compounds having thegeneral formula:R⁸—Z—(CH₂CH₂O)_(s)Bwherein R⁸ is an alkyl group or an alkyl aryl group, selected from thegroup consisting of primary, secondary and branched chain alkylhydrocarbyl groups, primary, secondary and branched chain alkenylhydrocarbyl groups, and/or primary, secondary and branched chain alkyl-and alkenyl-substituted phenolic hydrocarbyl groups having from about 6to about 20 carbon atoms, preferably from about 8 to about 18, morepreferably from about 10 to about 15 carbon atoms; s is an integer fromabout 2 to about 45, preferably form about 2 to about 20, morepreferably from about 2 to about 15; B is a hydrogen, a carboxylategroup, or a sulfate group; and linking group Z is —O—, —C(O)O—,—C(O)N(R)—, or —C(O)N(R)—, and mixtures thereof, in which R, whenpresent, is R⁸ or hydrogen.

The nonionic surfactants herein are characterized by an HLB(hydrophilic-lipophilic balance) of from 5 to 20, preferably from 6 to15.

Nonlimiting examples of preferred ethoxylated surfactant are:

-   -   straight-chain, primary alcohol ethoxylates, with R⁸ being        C₈-C₁₈ alkyl and/or alkenyl group, more preferably C₁₀-C₁₄, and        a s being from about 2 to about 8, preferably from about 2 to        about 6;    -   straight-chain, secondary alcohol ethoxylates, with R⁸ being        C₈-C_(˜)alkyl and/or alkenyl, e.g., 3-hexadecyl, 2-octadecyl,        4-eicosanyl, and 5-eicosanyl, and a s being from about 2 to        about 10;    -   alkyl phenol ethoxylates wherein the alkyl phenols having an        alkyl or alkenyl group containing from 3 to 20 carbon atoms in a        primary, secondary or branched chain configuration, preferably        from 6 to 12 carbon atoms, and s is from about 2 to about 12,        preferably from about 2 to about 8;    -   branched chain alcohol ethoxylates, wherein branched chain        primary and secondary alcohols (or Guerbet alcohols) which are        available, e.g., from the well-known “OXO” process or        modification thereof are ethoxylated.

Especially preferred are alkyl ethoxylate surfactants with each R⁸ beingC₈-C₁₆ straight chain and/or branch chain alkyl and the number ofethyleneoxy groups s being from about 2 to about 6, preferably fromabout 2 to about 4, more preferably with R⁸ being C₈-C₁₅ alkyl and sbeing from about 2.25 to about 3.5. These nonionic surfactants arecharacterized by an HLB of from 6 to about 11, preferably from about 6.5to about 9.5, and more preferably from 7 to about 9. Nonlimitingexamples of commercially available preferred surfactants are Neodol91-2.5 (C₉-C₁₀, s=2.7, HLB=8.5), Neodol 23-3 (C₁₂-C₁₃, s=2.9, HLB=7.9)and Neodol 25-3 (C₁₂-C₁₅, s=2.8, HLB=7.5). It is found, verysurprisingly, that these preferred surfactants which are themselves notvery water soluble (0.1% aqueous solutions of these surfactants are notclear), can at low levels, effectively dissolve and/or disperse shaperetention polymers such as copolymers containing acrylic acid andtert-butyl acrylate and silicone-containing copolymers into clearcompositions, even without the presence of a low molecular weightalcohol.

Also preferred is a nonionic surfactant from the group consisting offatty acid (C₁₂₋₁₈) esters of ethoxylated (EO₅₋₁₀₀) sorbitans. Morepreferably said surfactant is selected from the group consisting ofmixtures of laurate esters of sorbitol and sorbitol anhydrides; mixturesof stearate esters of sorbitol and sorbitol anhydrides; and mixtures ofoleate esters of sorbitol and sorbitol anhydrides. Even more preferablyand surfactant is selected from the group consisting of Polysorbate 20,which is a mixture of laurate esters of sorbitol and sorbitol anhydridesconsisting predominantly of the monoester, condensed with about 20 molesof ethylene oxide, Polysorbitol 60 which is a mixture of stearate estersof sorbitol and sorbitol anhydride, consisting predominantly of themonoester, condensed with about 20 moles of ethylene oxide; Polysorbate80 which is a mixture of oleate esters of sorbitol and sorbitolanhydrides, consisting predominantly of the monoester, condensed withabout 20 moles of ethylene ozide, and mixtures thereof. Most preferably,said surfactant is Polysorbate 60.

Other examples of preferred ethoxylated surfactant include carboxylatedalcohol ethoxylate, also known as ether carboxylate, with R⁸ having fromabout 12 to about 16 carbon atoms and s being from about 5 to about 13;ethoxylated quaternary ammonium surfactants, such as PEG-5 concomoniummethosulfate, PEG-15 concomonium chloride, PEG-15 oleammonium chlorideand bis(polyethoxyethanol)tallow ammonium chloride.

Other suitable nonionic ethoxylated surfactants are ethoxylated alkylamines derived from the condensation of ethylene oxide with hydrophobicalkyl amines, with R⁸ having from about 8 to about 22 carbon atoms and sbeing from about 3 to about 30.

Also suitable nonionic ethoxylated surfactants for use herein arealkylpolysaccharides which are disclosed in U.S. Pat. No. 4,565,647,Llenado, issued Jan. 21, 1986, incorporated herein by reference, havinga hydrophobic group containing from about 8 to about 30 carbon atoms,preferably from about 10 to about 16 carbon atoms and a polysaccharide,e.g., a polyglycoside, hydrophilic group containing from about 1.3 toabout 10, preferably from about 1.3 to about 3, most preferably fromabout 1.3 to about 2.7 saccharide units. Any reducing saccharidecontaining 5 or 6 carbon atoms can be used, e.g., glucose, galactose andgalactosyl moieties can be substituted for the glucosyl moieties. Theintersaccharide bonds can be, e.g., between the one position of theadditional saccharide units and the 2-, 3-, 4-, and/or 6- positions onthe preceding saccharide units. The preferred alkylpolyglycosides havethe formulaR²O(C_(n)H_(2n)O)t(glycosyl)_(x)wherein R² is selected from the group consisting of alkyl, alkylphenyl,hydroxyalkyl, hydroxyalkylphenyl, and mixtures thereof in which thealkyl groups contain from 10 to 18, preferably from 12 to 14, carbonatoms; n is 2 or 3, preferably from about 1.3 to about 3, mostpreferably from about 1.3 to about 2.7. The glycosol is preferablyderived from glucose.Odor Control Agent

The agents for odor control are of the type disclosed in U.S. Pat. Nos.5,534,165; 5,578,563; 5,663,134; 5,668,097; 5,670,475; and 5,714,137,Trinh et al. issued Jul. 9, 1996; Nov. 26, 1996; Sep. 2, 1997; Sep 16,1997; Sep. 23, 1997; and Feb. 3, 1998 respectively, all of said patentsbeing incorporated herein by reference. Fabric care compositions of thepresent invention can contain several different optional odor controlagents, preferably cyclodextrins, water soluble zinc salts, watersoluble copper salts, and mixtures thereof.

(a). Cyclodextrin

As used herein, the term “cyclodextrin” includes any of the knowncyclodextrins such as unsubstituted cyclodextrins containing from six totwelve glucose units, especially, alpha-cyclodextrin, beta-cyclodextrin,gamma-cyclodextrin and/or their derivatives and/or mixtures thereof. Thealpha-cyclodextrin consists of six glucose units, the beta-cyclodextrinconsists of seven glucose units, and the gamma-cyclodextrin consists ofeight glucose units arranged in donut-shaped rings. The specificcoupling and conformation of the glucose units give the cyclodextrins arigid, conical molecular structures with hollow interiors of specificvolumes. The “lining” of each internal cavity is formed by hydrogenatoms and glycosidic bridging oxygen atoms; therefore, this surface isfairly hydrophobic. The unique shape and physical-chemical properties ofthe cavity enable the cyclodextrin molecules to absorb (form inclusioncomplexes with) organic molecules or parts of organic molecules whichcan fit into the cavity. Many odorous molecules can fit into the cavityincluding many malodorous molecules and perfume molecules. Therefore,cyclodextrins, and especially mixtures of cyclodextrins with differentsize cavities, can be used to control odors caused by a broad spectrumof organic odoriferous materials, which may, or may not, containreactive functional groups. The complexation between cyclodextrin andodorous molecules occurs rapidly in the presence of water. However, theextent of the complex formation also depends on the polarity of theabsorbed molecules. In an aqueous solution, strongly hydropholicmolecules (those which are highly water-soluble) are only partiallyabsorbed, if at all. Therefore, cyclodextrin does not complexeffectively with some very low molecular weight organic amines and acidswhen they are present at low levels on wet fabrics. As the water isbeing removed however, e.g., the fabric is being dried off, some lowermolecular weight organic amines and acids have more affinity and willcomplex with the cyclodextrins more readily.

The cavities within the cyclodextrin in the solution of the presentinvention should remain essentially unfilled (the cyclodextrin remainsuncomplexed) while in solution, in order to allow the cyclodextrin toabsorb various odor molecules when the solution is applied to a surface.Non-derivatised (normal) beta-cyclodextrin can be present at a level upto its solubility limit of about 1.85% (about 1.85 g in 100 grams ofwater) at room temperature. Beta-cyclodextrin is not preferred incompositions which call for a level of cyclodextrin higher than itswater solubility limit. Non-derivatised beta-cyclodextrin is generallynot preferred when the composition contains surfactant since it affectsthe surface activity of most of the preferred surfactants that arecompatible with the derivatised cyclodextrins.

Preferably, the odor absorbing solution of the present invention isclear. The term “clear” as defined herein means transparent ortranslucent, preferably transparent, as in “water clear,” when observedthrough a layer having a thickness of less than about 10 cm.

Preferably, the cyclodextrins used in the present invention are highlywater-soluble such as, alpha-cyclodextrin and/or derivatives thereof,gamma-cyclodextrin and/or derivatives thereof, derivatisedbeta-cyclodextrins, and/or mixtures thereof. The derivatives ofcyclodextrins consist mainly of molecules wherein some of the OH groupsare converted to OR groups. Cyclodextrin derivatives includes, e.g.,those with short chain alkyl groups such as methylated cyclodextrins,and ethylated cyclodextrins, wherein R is a methyl or an ethyl group;those with hydroxyalkyl substituted groups, such as hydroxypropylcyclodextrins and/or hydroxyethyl cyclodextrins, wherein R is a—CH₂—CH(OH)—CH₃ or a —CH₂—CH₂—OH group; branched cyclodextrins such asmaltose-bonded cyclodextrins; cationic cyclodextrins such as thosecontaining 2-hydroxy-3-(dimethylamino)propyl ether, wherein R isCH₂—CH(OH)—CH₂—N(CH₃)₂ which is cationic at low pH; quaternary ammonium,e.g., 2-hydroxy-3-(trimethylammonio)propyl ether chloride groups,wherein R is CH₂—CH(OH)—CH₂—N⁺(CH₃)₃Cl⁻; anionic cyclodextrins such ascarboxymethyl cyclodextrins, cyclodextrin sulfates, and cyclodextrinsuccinylates; amophoteric cyclodextrins such ascarboxymethyl/quarternary ammonium cyclodextrins; cyclodextrins whereinat least one glucopyranose unit has a 3-6-anhydro-cyclomalto structure,e.g., the mono-3-6-anhydrocyclodextrins, as disclosed in “OptimalPerformances with Minimal Chemical Modification of Cyclodextrins”, F.Diedaini-Pilard and B. Perly, The 7th Intenational CyclodextrinSymposium Abstracts, Apr. 1994, p. 49, said reference being incorporatedherein by reference; and mixtures thereof. Other cyclodextrinderivatives are disclosed in U.S. Pat. Nos.: 3,426,011, Parmerter etal., issued Feb. 4, 1969; 3,453,257; 3,453,258; 3,453,258; 3,453,259;and 3,453,260, all in the names of Parmerter et al., and all issued Jul.1, 1969; 3,459,731, Gramera et al., issued Aug. 5, 1969; 3,553,191,Parmerter et al., issued Jan. 5, 1971; 3,565,887, Parmerter et al.,issued Feb. 23, 1971; 4,535,152, Szejtli et al., issued Aug. 13, 1985;4,616,008, Hirai et al., issued Oct. 7, 1986; 4,678,598, Ogino et al.,issued Jul. 7, 1987; 4,638,058, Brandt et al., issued Jan. 20, 1987; and4,746,734, Tsuchiyama et al., issued May 24, 1988; all of said patentsbeing incorporated herein by reference.

Highly water-soluble cyclodextrins are those having water solubility ofat least about 10 g in 100 ml of water at room temperature, preferablyat least about 20 g in 100 ml of water, more preferably at least about25 g in 100 ml of water at room temperature. The availability ofsolubilized, uncomplexed cyclodextrins is essential for effective andefficient odor control performance. Solubilized, water-solublecyclodextrin can exhibit more efficient odor control performance thannon-water-soluble cyclodextrin when deposited onto surfaces, especiallyfabric.

Examples of preferred water-soluble cyclodextrin derivatives suitablefor use herein are hydroxypropyl alpha-cyclodextrin, methylatedalpha-cyclodextrin, methylated beta-cyclodextrin hydroxyethylbeta-cyclodextrin, and hydroxypropyl beta-cyclodextrin. Hydroxyalkylcyclodextrin derivatives preferably have a degree of substitution offrom about 1 to about 14, more preferably from about 1.5 to about 7,wherein the total number of OR groups per cyclodextrin is defined as thedegree of substitution. Methylated cyclodextrin derivatives typicallyhave a degree of substitution of from about 1 to about 18, preferablyfrom about 3 to about 16. A known methylated beta-cyclodextrin isheptakis-2,6-di-O-methyl-β-cyclodextrin, commonly known as DIMEB, inwhich each glucose unit has about 2 methyl groups with a degree ofsubstitution of about 14. A preferred, more commercially available,methylated beta-cyclodextrin is a randomly methylated beta-cyclodextrin,commonly known as RAMEB, having different degrees of substitution,normally of about 12.6. RAMEB is more preferred than DIMEB, since DIMEBaffects the surface activity of the preferred surfactants more thanRAMEB. The preferred cyclodextrins are available, e.g., from CerestarUSA, Inc., and Wacker Chemicals (USA), Inc.

It is also preferable to use a mixture of cyclodextrins. Such mixturesabsorb odors more broadly by complexing with a wider range ofodoriferous molecules having a wider range of molecular sizes.Preferably at least a portion of the cyclodextrins is alpha-cyclodextrinand its derivatives thereof, gamma-cyclodextrin and its derivativesthereof, and/or derivatised beta-cyclodextrin, more preferably a mixtureof alpha-cyclodextrin, or an alpha-cyclodextrin derivative, andderivatised beta-cyclodextrin, even more preferably a mixture ofderivatised alpha-cyclodextrin and derivatised beta-cyclodextrin, mostpreferably a mixture of hydroxypropyl alpha-cyclodextrin andhydroxypropyl beta-cyclodextrin, and/or a mixture of methylatedalpha-cyclodextrin and methylated beta-cyclodextrin.

For controlling odor on fabrics, the composition is preferably used as aspray. It is preferable that the usage compositions of the presentinvention contain low levels of cyclodextrin so that a visible staindoes not appear on the fabric at normal usage levels. Preferably, thesolution used to treat the surface under usage conditions is virtuallynot discernible when dry. Typical levels of cyclodextrin in usagecompositions for usage conditions are from about 0.01% to about 5%,preferably from about 0.1% to about 4%, more preferably from about 0.5%to about 2% by weight of the composition. Compositions with higherconcentrations can leave unacceptable visible stains on fabrics as thesolution evaporates off of the fabric. This is especially a problem onthin, colored, synthetic fabrics. In order to avoid or minimize theoccurrence of fabric staining, it is preferable that the fabric betreated at a level of less than about 5 mg of cyclodextrin per gram offabric, more preferably less than about 2 mg of cyclodextrin per gram offabric. The presence of the surfactant can improve appearance byminimizing localized spotting.

When the optional cyclodextrin is present in the composition, thepolymer active in the composition of the present invention should becyclodextrin-compatible, that is it should not substantially formcomplexes with cyclodextrin so as to diminish performance of thecyclodextrin and/or the polymer. Complex formation affects both theability of the cyclodextrin to absorb odors and the ability of thepolymer to impart color renewal and/or shape retention to fabric. Inthis case, the monomers having pendant groups that can complex withcyclodextrin are not preferred because they can form complexes withcyclodextrin. Examples of such monomers are acrylic or methacrylic acidesters of C₇-C₁₈ alcohols, such as neodecanol, 3-heptanol, benzylalcohol 2-octanol, 6-methyl-1-heptanol, 2-ethyl-1-hexanol,3,5-dimethyl-1-hexanol, 3,5,5-trimethyl-1-hexanol, and 1-decanol;aromatic vinyls, such as styrene; t-butylstyrene; vinyl toluene; and thelike.

Low Molecular Weight Polyols

Low molecular weight polyols with relatively high boiling points, ascompared to water, such as ethylene glycol, propylene glycol and/orglycerol are preferred optional ingredients for improving odor controlperformance of the composition of the present invention whencyclodextrin is present. Not to be bound by theory, it is believed thatthe incorporation of a small amount of low molecular weight glycols intothe composition of the present invention enhances the formation of thecyclodextrin inclusion complex as the fabric dries.

It is believed that the polyols' ability to remain on the fabric for alonger period of time the water, as the fabric dries allows it to formternary complexes with the cyclodextrin and some malodorous molecules.The addition of the glycols is believed to fill up void space in thecyclodextrin cavity that is unable to be field by some malodor moleculesof relatively smaller sizes. Preferably the glycol used is glycerin,ethylene glycol, propylene glycol, diethylene glycol, dipropylene glycolor mixtures thereof, more preferably ethylene glycol an/or propyleneglycol. Cyclodextrins prepared by processes that result in a level ofsuch polyols are highly desirable, since they can be used withoutremoval of the polyols.

Some polyols, e.g., dipropylene glcyol, are also useful to facilitatethe solubilization of some perfume ingredients in the composition of thepresent invention.

Typically, glcyol is added to the composition of the present inventionat a level of from about 0.01% to about 3%, by weight of thecomposition, preferably from about 0.05% to about 1%, more preferablyfrom about 0.1% to about 0.5%, by weight of the composition. Thepreferred weight ratio of low molecular weight polyol to cyclodextirn isfrom about 2:1,000 to about 20:100, more preferably from about 3:1,000to about 15:100, even more preferably from about 5:1,000 to about10:100, and most preferably from about 1:100 to about 7:100.

(b) Metal Salts

Optionally, but highly preferred, the present invention can includemetallic salts for added odor absorption and/or antimicrobial benefitfor the cyclodextrin solution when cyclodextrin is present. The metallicsalts are selected from the group consisting of copper salts, zincsalts, and mixtures thereof.

Copper salts have some antimicrobial benefits. Specifically, cupricabietate acts as a fungicide, copper acetate acts as a mildew inhibitor,cupric chloride acts as a fungicide, copper lactate acts as a fungicide,and copper sulfate acts as a germicide. Copper salts also possess somemalodor control abilities. See U.S. Pat. No. 3,172,817, Leupold, et al.,which discloses deodorizing compositions for treating disposablearticles, comprising at least slightly water-soluble salts ofacylacetone, including copper salts and zinc salts, all of said patentsare incorporated herein by reference.

The preferred zinc salts possess malodor control abilities. Zinc hasbeen used most often for its ability to ameliorate malodor, e.g., inmouth wash products, as disclosed in U.S. Pat. Nos. 4,325,939, issuedApr. 20, 1982 and 4,469,674, issued Sep. 4, 1983, to N. B. Shah, et al.,all of which are incorporated herein by reference. Highly-ionized andsoluble zinc salts such as zinc chloride, provide the best source ofzinc ions. Zinc borate functions as a fungistat and a mildew inhibitor,zinc caprylate functions as a fungicide, zinc chloride providesantiseptic and deodorant benefits, zinc ricinoleate functions as afungicide, zinc sulfate heptahydrate functions as a fungicide and zincundecylenate functions as a fungistat.

Preferably the metallic salts are water-soluble zinc salts, copper saltsor mixtures thereof, and more preferably zinc salts, especially ZnCl₂.These salts are preferably present in the present invention primarily toabsorb amine and sulfur-containing compounds that have molecular sizestoo small to be effectively complexed with the cyclodextrin molecules.Low molecular weight sulfur-containing materials, e.g., sulfide andmercaptants, are components of many types of malodors, e.g., food odors(garlic, onion), body/perspiration odor, breath odor, etc. Low molecularweight amines are also components of many malodors, e.g., food odors,body odors, urine, etc.

When metallic salts are added to the composition of the presentinvention they are typically present at a level of from about 0.1% toabout 10%, preferably from about 0.2% to about 8%, more preferably fromabout 0.3% to about 5% weight of the usage composition. When zinc saltsare used as the metallic salt, and a clear solution is desired, it ispreferable that the pH of the solution is adjusted to less than about 7,more preferably less than about 6, most preferably, less than about 5,in order to keep the solution clear.

(c) Soluble Carbonate and/or Bicarbonate Salts

Water-soluble alkali metal carbonate and/or bicarbonate salts, such assodium bicarbonate, potassium bicarbonate, potassium carbonate, cesiumcarbonate, sodium carbonate, and mixtures thereof can be added to thecomposition of the present invention in order to help to control certainacid-type odors. Preferred salts are sodium carbonate monohydrate,potassium carbonate, sodium bicarbonate, potassium bicarbonate, andmixtures thereof. When these salts are added to the composition of thepresent invention, they are typically present at a level of from about0.1% to about 5%, preferably from about 0.2% to about 3%, morepreferably from about 0.3% to about 2%, by weight of the composition.When these salts are added to the composition of the present inventionit is preferably that incompatible metal salts not be present in theinvention. Preferably, when these salts are used the composition shouldbe essentially free of zinc and other incompatible metal ions, e.g., Ca,Fe, Ba, etc. which form water-insoluble salts.

(d) Mixtures Thereof

Mixtures of the above materials are desirable, especially when themixture provides control over a broader range of odors.

Perfume

The composition of the present invention can also optionally provide a“scent signal” in the form of a pleasant odor which provides a freshnessimpression to the treated fabrics. The scent signal can be designed toprovide a fleeting perfume scent. When perfume is added as a scentsignal, it is added only at very low levels, e.g., from about 0.001% toabout 0.5%, preferably from about 0.003% to about 0.3%, more preferablyfrom about 0.005% to about 0.2%, by weight of the usage composition.

Perfume can also be added as more intense odor in product and onfabrics. When stronger levels of perfume are preferred, relativelyhigher levels of perfume can be added.

Any type of perfume can be incorporated into the composition of thepresent invention. The preferred perfume ingredients are those suitablefor use to apply on fabrics and garments. Typical examples of suchpreferred ingredients are given in U.S. Pat. No. 5,445,747, issued Aug.29, 1995 to Kvietok et al., incorporated herein by reference.

When long lasting fragrance odor on fabrics is desired, it is preferredto use at least an effective amount of perfume ingredients which have aboiling point of about 240° C. or higher, preferably of about 250° C. orhigher. Nonlimiting examples of such preferred ingredients are given inU.S. Pat. No. 5,500,138, issued Mar. 19, 1996 to Bacon et al.,incorporated herein by reference. It is also preferred to use materialsthat an slowly release perfume ingredients after the fabric is treatedby the color improvement composition of this invention. Examples ofmaterials of this type are given in U.S. Pat. No. 5,531,910, Severns etal., issued Jul. 2, 1996, said patent being incorporated herein byreference.

When cyclodextrin is present, it is essential that the perfume be addedat a level wherein even if all of the perfume in the composition were tocomplex with the cyclodextrin molecules when cyclodextrin is present,there will still be an effective level of uncomplexed cyclodextrinmolecules present in the solution to provide adequate odor control. Inorder to reserve an effective amount of cyclodextrin molecules for odorcontrol when cyclodextrin is present, perfume is typically present at alevel wherein less than about 90% of the cyclodextrin complexes with theperfume, preferably less than about 50% of the cyclodextrin complexeswith the perfume, more preferably, less than about 30% of thecyclodextrin complexes with the perfume, and most preferably, less thanabout 10% of the cyclodextrin complexes with the perfume. Thecyclodextrin to perfume weight ratio should be greater than about 8:1,preferably greater than about 10:1, more preferably greater than about20:1, even more preferably greater than 40:1 and most preferably greaterthan about 70:1.

Preferably the perfume is hydrophilic and is composed predominantly ofingredients selected from two groups of ingredients, namely, (a)hydrophilic ingredients having a ClogP of less than about 3.5, morepreferably less than about 3.0, and (b) ingredients having significantlow detection threshold, and mixtures thereof. Typically, at least about50%, preferably at least about 60%, more preferably at least about 70%,and most preferably at least about 80% by weight of the perfume iscomposed of perfume ingredients of the above groups (a) and (b). Forthese preferred perfumes, the cyclodextrin to perfume weight ratio istypically of from about 2:1 to about 200:1; preferably from about 4:1 toabout 100:1, more preferably from about 6:1 to about 50:1, and even morepreferably from about 8:1 to about 30:1.

(a). Hydrophilic Perfume Ingredients

The hydrophilic perfume ingredients are more soluble in water, have lessof a tendency to complex with the cyclodextrins, and are more availablein the odor absorbing composition than the ingredients of conventionalperfumes. The degree of hydrophobicity of a perfume ingredient can becorrelated with its octanol/water partition coefficient P. Theoctanol/water partition coefficient of a perfume ingredient in the ratiobetween its equilibrium concentration in octanol and in water. A perfumeingredient with a greater partition coefficient P is considered to bemore hydrophobic. Conversely, a perfume ingredient with a smallerpartition coefficient P is considered to be more hydrophilic. Since thepartition coefficients of the perfume ingredients normally have highvalues, they are more conveniently given in the form of their logarithmto the base 10, logP. Thus the preferred perfume hydrophilic perfumeingredients of this invention have logP of about 3.5 or smaller,preferably of about 3.0 or smaller.

The logP of many perfume ingredients have been reported; for example,the Pomona92 database, available from Daylight Chemical InformationSystems, Inc. (Daylight CIS), Irvine, Calif., contains many, along withcitations to the original literature. However, the logP values are mostconveniently calculated by the “CLOGP” program, also available fromDaylight CIS. This program also lists experimental logP values when theyare available in the Pomona92 database. The “calculated logP” (ClogP) isdetermined by the fragment approach of Hansch and Leo (cf., A. Leo, inComprehensive Medicinal Chemistry, Vol. 4, C. Hansch, P. G. Sammens, J.B. Taylor and C. A. Ramsden, Eds., p. 295, Pergamon Press, 1990,incorporated herein by reference). The fragment approach is based on thechemical structure of each perfume ingredient, and takes into accountthe numbers and types of atoms, the atom connectivity, and chemicalbonding. The ClogP values, which are the most reliable and widely usedestimates for this physicochemical property, are used instead of theexperimental logP values in the selection of perfume ingredients whichare useful in the present invention.

Non-limiting examples of the more preferred hydrophilic perfumeingredients are allyl amyl glycolate, allyl caproate, amyl acetate, amylpropionate, anisic aldehyde, anisyl acetate, anisole, benzaldehyde,benzyl acetate, benzyl acetone, benzyl alcohol, benzyl formate, benzyliso valerate, benzyl propionate, beta gamma hexenol, calone, camphorgum, laevo-carveol, d-carvone, laevo-carvone, cinnamic alcohol, cinnamylacetate, cinnamic alcohol, cinnamyl formate, cinnamyl propionate,cis-jasmone, cis-3-hexenyl acetate, coumarin, cuminic alcohol, cuminicaldehyde, Cyclal C, cyclogalbanate, dihydroeuginol, dihydroisojasmonate, dimethyl benzyl carbonol, dimethyl benzyl carbinylacetate, ethyl acetate, ethyl aceto acetate, ethyl amyl ketone, ethylanthranilate, ethyl benzoate, ethyl butyrate, ethyl cinnamate, ethylhexyl ketone, ethyl maltol, ethyl-2-methyl butyrate, ethyl methylphenylglycidate, ethyl phenyl acetate, ethyl salicylate, ethyl vanilin,eucalyptol, eugenol, eugenyl aceate, eugenyl formate, eugenyl methylether, fenchyl alcohol, flor acetate (tricyclo decenyl acetate),fructone, frutene (tricyclo decenyl propionate), geraniol, geranyloxyacetaldehyde, heliotropin, hexenol, hexenyl acetate, hexyl acetate,hexyl formate, hinokitiol, hydrotropic alcohol, hydroxycitronellal,hydroxycitronellal diethyl acetal, hydroxycitronellol, indole, isoamylalcohol, iso cyclo citral, isoeugenol, isoeugenyl acetate, isomenthone,isopulegyl acetate, isoquinoline, keone, ligustral, linalool, linalooloxide, linalyl formate, lyral, menthone, methyl acetophenone, methylamyl ketone, methyl anthranilate, methyl benzoate, methyl benzylacetate, methyl cinnamate, methyl dihydrojasmonate, methyl eugenol,methyl heptenone, methyl heptine carbonate, methyl heptyl ketone, methylhexyl ketone, methyl isobutenyl tetrahydropyran, methyl-N-methylanthranilate, methyl beta naphthyl ketone, methyl phenyl carbinylacetate, methyl salicylate, nerol, nonalactone, octalactone, octylalcohol (octanol-2), para-anisic aldehyde, para-cresol, para-cresylmethyl ether, para hydroxy phenyl butanone, para-methoxy acetophenone,para-methyl acetophenone, phenoxy ethanol, phenoxyethyl propionate,phenyl acetaldehyde, phenylacetaldehyde diethyl ether, phenylethyloxyacetaldehyde, phenyl ethyl acetate, phenyl ethyl alcohol, phenylethyl dimethyl carbinol, prenyl acetate, propyl butyrate, pulegone, roseoxide, safrole, terpineol, vanillin, viridine, and mixtures thereof.

Nonlimiting examples of other preferred hydrophilic perfume ingredientswhich can be used in perfume compositions of this invention are allylheptoate, amyl benzoate, anethole, benzophenone, carvacrol, citral,citronellol, citronellyl nitrile, cyclohexyl ethyl acetate, cymal,4-decenal, dihydro isojasmonate, dihydro myrcenol, ethyl methyl phenylglycidate, fenchyl acetate, florhydral, gamma-nonalactone, geranylformate, geranyl nitrile, hexenyl isobutyrate, alpha-ionone, isobornylacetate, isobutyl benzoate, isononyl alcohol, isomenthol, para-isopropylphenylacetaldehyde, isopulegol, linalyl acetate, 2-methoxy naphthalene,menthyl acetate, methyl chavicol, musk ketone, beta naphthol methylether, neral, nonyl aldehyde, phenyl heptanol, phenyl hexanol, terpinylacetate, Veratrol, yara-yara, and mixtures thereof.

The preferred perfume compositions used in the present invention containat least 4 different hydrophilic perfume ingredients, preferably atleast 5 different hydrophilic perfume ingredients, more preferably atleast 6 different hydrophilic perfume ingredients, and even morepreferably at least 7 different hydrophilic perfume ingredients. Mostcommon perfume ingredients which are derived from natural sources arecomposed of a multitude of components. When each such material is usedin the formulation of the preferred perfume compositions of the presentinvention, it is counted as one single ingredient, for the purpose ofdefining the invention.

(b). Low Odor Detection Threshold Perfume Ingredients

The odor detection threshold of an odorous material is the lowest vaporconcentration of that material which can be olfactorily detected. Theodor detection threshold and some odor detection threshold values arediscussed in, e.g., “Standardized Human Olfactory Thresholds”, M. Devoset al, IRL Press at Oxford University Press, 1990, and “Compilation ofOdor and Taste Threshold Values Data”, F. A. Fazzalari, editor, ASTMData Series DS 48A, American Society for Testing and Materials, 1978,both of said publications being incorporated by reference. The use ofsmall amounts of perfume ingredients that have low odor detectionthreshold values can improve perfume odor character, even though theyare not as hydrophilic as perfume ingredients of group (a) which aregiven hereinabove. Perfume ingredients that do not belong to group (a)above, but have a significantly low detection threshold, useful in thecomposition of the present invention, are selected from the groupconsisting of ambrox, bacdanol, benzyl salicylate, butyl anthranilate,cetalox, damascenone, alpha-damascone, gamma-dodecalactone, ebanol,herbavert, cis-3-hexenyl salicylate, alpha-ionone, beta-ionone,alpha-isomethylionone, lilial, methyl nonyl ketone, gamma-undecalactone,undecylenic aldehyde, and mixtures thereof. These materials arepreferably present at low levels in addition to the hydrophilicingredients of group (a), typically less than about 20%, preferably lessthan about 15%, more preferably less than about 10%, by weight of thetotal perfume compositions of the present invention. However, only lowlevels are required to provide an effect.

There are also hydrophilic ingredients of group (a) that have asignificantly low detection threshold, and are especially useful in thecomposition of the present invention. Examples of these ingredients areallyl amyl glycolate, anethole, benzyl acetone, calone, cinnamicalcohol, coumarin, cyclogalbanate, Cyclal C, cymal, 4-decenal, dihydroisojasmonate, ethyl anthranilate, ethyl-2-methyl butyrate, ethylmethylphenyl glycidate, ethyl vanillin, eugenol, flor acetate,florhydral, fructone, frutene, heliotropin, keone, indole, iso cyclocitral, isoeugenol, lyral, methyl heptine carbonate, linalool, methylanthranilate, methyl dihydrojasmonate, methyl isobutenyltetrahydropyran, methyl beta naphthyl ketone, beta naphthol methylether, nerol, para-anisic aldehyde, para hydroxy phenyl butanone, phenylacetaldehyde, vanillin, and mixtures thereof. Use of low odor detectionthreshold perfume ingredients minimizes the level of organic materialthat is released into the atmosphere.

Antimicrobial Active

Optionally, the color improvement composition of the present inventioncomprise an effective amount, to kill, or reduce the growth of microbes,of antimicrobial active; preferably from about 0.001% to about 2%, morepreferably from about 0.002% to about 1%, even more preferably fromabout 0.003% to about 0.3%, by weight of the usage composition. Theeffective antimicrobial active can function as disinfectants/sanitizers,and is useful in providing protection against organisms that becomeattached to the fabrics.

Given below are nonlimiting examples of antimicrobial actives which areuseful in the present invention: Pyrithiones, especially the zinccomplex (ZPT); Octopirox; parabens, including methylparaben,propylparaben, butylparaben, ethylparaben, isopropylparaben,isobutylparaben, benzylparaben, sodium methylparaben, and sodiumpropylparaben; DMDM hydantoin (Glydant);methylchloroisothiazolinone/methylisothiazolinone (Kathon CG); sodiumsulfite; sodium bisulfite; imidazolidinyl urea; diazolidinyl urea(Germail 2); sorbic acid/potassium sorbate; dehydroacetic acid/sodiumdehydroacetate; benzyl alcohol; sodium borate;2-bromo-2-nitropropane-1,3-diol (Bronopol); formalin; iodopropynylbutylcarbamate; boric acid; chloroacetamide; methenamine; methyldibromoglutaronitrile; glutaraldehyde; hexamidine isethionate;5-bromo-5-nitro-1,3-dioxane; phenethyl alcohol; o-phenylphenol/sodiumo-phenylphenol; sodium hydroxymethylglycinate; polymethoxy bicyclicoxazolidine; dimethoxane; thimersol; dichlorobenzyl alcohol; captan;chlorphenenesin; dichlorophene; chlorbutanol; phenoxyethanol;phenoxyisopropanol; halogenated diphenyl ethers;2,4,4′-trichloro-2′-hydroxy-diphenyl ether (Triclosan);2,2′-dihydroxy-5,5′-dibromo-diphenyl ether;

Phenolic Compounds—(including phenol and its homologs, mono- andpoly-alkyl and aromatic halophenols, resorcinol and its derivatives,bisphenolic compounds and halogenated salicylanilides); phenol and itshomologs including phenol, 2-methyl phenol, 3-methyl phenol, 4-methylphenol, 4-ethyl phenol, 2,4-dimethyl phenol, 2,5-dimethyl phenol,3,4-dimethyl phenol, 2,6-dimethyl phenol, 4-n-propyl phenol, 4-n-butylphenol, 4-n-amyl phenol, 4-tert-amyl phenol, 4-n-hexyl phenol, and4-n-heptyl phenol; mono- and poly-alkyl and aromatic halophenolsincluding p-chlorophenol, methyl p-chlorophenol, ethyl p-chlorophenol,n-propyl p-chlorophenol, n-butyl p-chlorophenol, n-amyl p-chlorophenol,sec-amyl p-chlorophenol, n-hexyl p-chlorophenol, cyclohexylp-chlorophenol, n-heptyl p-chlorophenol, n-octyl p-chlorophenol,o-chlorophenol, methyl o-chlorophenol, ethyl o-chlorophenol, n-propylo-chlorophenol, n-butyl o-chlorophenol, n-amyl o-chlorophenol, tert-amylo-chlorophenol, n-hexyl o-chlorophenol, n-heptyl o-chlorophenol,o-benzyl p-chlorophenol, o-benzyl-m-methyl p-chlorophenol, o-benzyl-m,m-dimethyl p-chlorophenol, o-phenylethyl p-chlorophenol,o-phenylethyl-m-methyl p-chlorophenol, 3-methyl p-chlorophenol,3,5-dimethyl p-chlorophenol, 6-ethyl-3-methyl p-chlorophenol,6-n-propyl-3-methyl p-chlorophenol, 6-iso-propyl-3-methylp-chlorophenol, 2-ethyl-3,5-dimethyl p-chlorophenol,6-sec-butyl-3-methyl p-chlorophenol, 2-iso-propyl-3,5-dimethylp-chlorophenol, 6-diethylmethyl-3-methyl p-chlorophenol,6-iso-propyl-2-ethyl-3-methyl p-chlorophenol, 2-sec-amyl-3,5-dimethylp-chlorophenol, 2-diethylmethyl-3,5-dimethyl p-chlorophenol,6-sec-octyl-3-methyl p-chlorophenol, p-chloro-m-cresol, p-bromophenol,methyl p-bromophenol, ethyl p-bromophenol, n-propyl p-bromophenol,n-butyl p-bromophenol, n-amyl p-bromophenol, sec-amyl p-bromophenol,n-hexyl p-bromophenol, cyclohexyl p-bromophenol, o-bromophenol,tert-amyl o-bromophenol, n-hexyl o-bromophenol, n-propyl-m,m-dimethylo-bromophenol, 2-phenyl phenol, 4-chloro-2-methyl phenol,4-chloro-3-methyl phenol, 4-chloro-3,5-dimethyl phenol,2,4-dichloro-3,5-dimethylphenol, 3,4,5,6-terabromo-2-methylphenol,5-methyl-2-pentylphenol, 4-isopropyl-3-methylphenol,para-chloro-meta-xylenol (pcmx), 5-chloro-2-hydroxydiphenylmethane;resorcinol and its derivatives including resorcinol, methyl resorcinol,ethyl resorcinol, n-propyl resorcinol, n-butyl resorcinol, n-amylresorcinol, n-hexyl resorcinol, n-heptyl resorcinol, n-octyl resorcinol,n-nonyl resorcinol, phenyl resorcinol, benzyl resorcinol, phenylethylresorcinol, phenylpropyl resorcinol, p-chlorobenzyl resorcinol, 5-chloro2,4-dihydroxydiphenyl methane, 4′-chloro 2,4-dihydroxydiphenyl methane,5-bromo 2,4-dihydroxydiphenyl methane, and 4′-bromo2,4-dihydroxydiphenyl methane; bisphenolic compounds including 2,2′-,methylene bis (4-chlorophenol), 2,2′-methylene bis(3,4,6-trichlorophenol), 2,2′-methylene bis (4-chloro-6-bromophenol),bis (2-hydroxy-3,5-dichlorophenyl) sulphide, and bis(2-hydroxy-5-chlorobenzyl)sulphide; benzoic esters includingp-hydroxybenzoic acid, methyl p-hydroxybenzoic acid, ethylp-hydroxybenzoic acid, propyl p-hydroxybenzoic acid, and butylp-hydroxybenzoic acid.

Another class of antibacterial agents, which are useful in the presentinvention, are the so-called “natural” antibacterial actives, referredto as natural essential oils. These actives derive their names fromtheir natural occurrence in plants. Typical natural essential oilantibacterial actives include oils of anise, lemon, orange, rosemary,wintergreen, thyme, lavender, cloves, hops, tea tree, citronella, wheat,barley, lemongrass, cedar leaf, cedarwood, cinnamon, fleagrass,geranium, sandalwood, violet, cranberry eucalyptus, vervain, peppermint,gum benzoin, Hydastis carradensis, Berberidaceae daceae, Ratanhiae andCurcuma longa. Also included in this class of natural essential oils arethe key chemical components of the plant oils which have been found toprovide the antimicrobial benefit. These chemicals include, but are notlimited to anethol, catechole, camphene, thymol, eugenol, eucalyptol,ferulic acid, farnesol, hinokitiol, tropolone, limonene, menthol, methylsalicylate, salicylic acid, thymol, terpineol, verbenone, berberine,ratanhiae extract, caryophellene oxide, citronellic acid, curcumin,nerolidol, geraniol and benzoic acid.

Additional active agents are antibacterial metal salts. This classgenerally includes salts of metals in groups 3b-7b, 8 and 3a-5a.Specifically are the salts of aluminum, zirconium, zinc, silver, gold,copper, lanthanum, tin, mercury, bismuth, selenium, strontium, scandium,yttrium, cerium, praseodymiun, neodymium, promethum, samarium, europium,gadolinium, terbium, dysprosium, holmium, erbium, thulium, ytterbium,lutetium and mixtures thereof.

Preferred antimicrobial agents for use herein are the broad spectrumactives selected from the group consisting of Triclosan,phenoxyisopropanol, phenoxyethanol, PCMX, natural essential oils andtheir key ingredients, and mixtures thereof. The most preferredantimicrobial active for use in the present invention is Triclosan.

Quaternary Compounds

A wide range of quaternary compounds can also be used as antimicrobialactives, in conjunction with the preferred surfactants, for compositionsof the present invention. Non-limiting examples of useful quarternarycompounds include: (1) benzalkonium chlorides and/or substitutedbenzalkonium chlorides such as commercially available Barquat®(available from Lonza), Maquat® (available from Mason), Variquat®(available from Witco/Sherex), and Hyamine® (available from Lonza); (2)di(C₆-C₁₄)alkyl di-short chain (C₁₋₄ alkyl and/or hydroxyalkyl)quaternary such as Bardac® products of Lonza. These quaternary compoundscontain two relatively short chains, e.g., C₁₋₄ alkyl and/or hydroxyalkyl groups and two C₆₋₁₂, preferably C₆₋₁₀, and more preferably C₈,alkyl groups, (3) N-(3-chloroallyl) hexaminium chlorides such asDowicide® and Dowicil® available from Dow; (4) benzethonium chloridesuch as Hyamine® 1622 from Rohm & Haas; (5) methylbenzethonium chloriderepresented by Hyamine® 10× supplied by Rohm & Hass, (6) cetylpyridiniumchloride such as Cepacol chloride available from of Merrell Labs.Examples of the preferred dialkyl quaternary compounds aredi(C₈-C₁₂)dialkyl dimethyl ammonium chloride, such asdidecyldimethylammonium chloride (Bardac 22), anddioctyldimethylammonium chloride (Bardac 2050). Typical concentrationsfor biocidal effectiveness of these quaternary compounds range fromabout 0.001% to about 0.8%, preferably from about 0.005% to about 0.3%,more preferably from about 0.01% to 0.2%, by weight of the usagecomposition. The corresponding concentrations for the concentratedcompositions are from about 0.003% to about 2%, preferably from about0.006% to about 1.2%, and more preferably from about 0.1% to about 0.8%by weight of the concentrated compositions.

When cyclodextrin is present, the solubilized, water-solubleantimicrobial active is useful in providing protection against organismsthat become attached to the treated fabrics. The antimicrobial should becyclodextrin-compatible, e.g., not substantially forming complexes withthe cyclodextrin in the odor absorbing composition when cyclodextrin ispresent. The free, uncomplexed antimicrobial, e.g., antibacterial,active provides an optimum antibacterial performance.

Sanitization of fabrics can be achieved by the compositions of thepresent invention containing, antimicrobial materials, e.g.,antibacterial halogenated compounds, quaternary compounds, and phenoliccompounds. Some of the more robust cyclodextrin-compatible antimicrobialhalogenated compounds which can function as disinfectants/sanitizers aswell as finish product preservatives (vide infra), and are useful in thecompositions of the present invention include 1,1′-hexamethylenebis(5-p-chlorophenyl)biguanide), commonly known as chlorhexidine, andits salts, e.g., with hydrochloric, acetic and gluconic acids. Thedigluconate salt is highly water-soluble, and 70% in water, and thediacetate salt has a solubility of about 1.8% in water. Whenchlorhexidine is used as a sanitizer in the present invention it istypically present at a level of from about 0.001% to about 0.4%,preferably from about 0.002% to about 0.3%, and more preferably fromabout 0.05% to about 0.2%, by weight of the usage composition. In somecases, a level of from about 1% to about 2% may be needed for virucidalactivity.

Aminocarboxylate Chelators

Chelators, e.g., ethylenediaminetetraacetic acid (EDTA),hydroxyethylenediaminetriacetic acid, diethylenetriaminepentaaceticacid, and other aminocarboxylate chelators, and mixtures thereof, andtheir salts, and mixtures thereof, can optionally be used to increaseantimicrobial and preservative effectiveness against Gram-negativebacteria, especially Pseudomonas species. Although sensitivity to EDTAand other aminocarboxylate chelators is mainly a characteristic ofPseudomonas species, other bacterial species highly susceptible tochelators include Achromobacter, Alcaligenes, Azotobacter, Escherichia,Salmonella, Spirillum, and Vibrio. Other groups of organisms also showincreased sensitivities to these chelators, including fungi and yeasts.Furthermore, aminocarboxylate chelators can help, e.g., maintainingproduct clarity, protecting fragrance and perfume components, andpreventing rancidity and off odors.

Although these aminocarboxylate chelators may not be potent biocides intheir own right, they function as potentiators for improving theperformance of other antimicrobials/preservatives in the compositions ofthe present invention. Aminocarboxylate chelators can potentiate theperformance of many of the cationic, anionic, and nonionicantimicrobials/preservatives, phenolic compounds, and isothiazolinones,that are used as antimicrobials/preservatives in the composition of thepresent invention. Nonlimiting examples of cationicantimicrobials/preservatives potentiated by aminocarboxylate chelatorsin solutions are chlorhexidine salts (including digluconate, diacetate,and dihydrochloride salts), and Quaternium-15, also known as Dowicil200, Dowicide Q, Preventol D1, benzalkonium chloride, cetrimonium,myristalkonium chloride, cetylpyridinium chloride, lauryl pyridiniumchloride, and the like. Nonlimiting examples of useful anionicantimicrobials/preservatives which are enhanced by aminocarboxylatechelators are sorbic acid and potassium sorbate. Nonlimiting examples ofuseful nonionic antimicrobials/preservatives which are potentiated byaminocarboxylate chelators are DMDM hydantoin, phenethyl alcohol,monolaurin, imidazolidinyl urea, and Bronopol(2-bromo-2-nitropropane-1,3-diol).

Examples of useful phenolic antimicrobials/preservatives potentiated bythese chelators are chloroxylenol, phenol, tert-butyl hydroxyanisole,salicylic acid, resorcinol, and sodium o-phenyl phenate. Nonlimitingexamples of isothiazolinone antimicrobials/preservatives which areenhanced by aminocarboxylate chelators are Kathon, Proxel and Promexal.

The optional chelators are present in the compositions of this inventionat levels of, typically, from about 0.01% to about 0.3%, more preferablyfrom about 0.02% to about 0.1%, most preferably from about 0.02% toabout 0.05% by weight of the usage compositions to provide antimicrobialefficacy in this invention.

Free, uncomplexed aminocarboxylate chelators are required to potentiatethe efficacy of the antimicrobials. Thus, when excess alkaline earth(especially calcium and magnesium) and transitional metals (iron,manganese, copper, and others) are present, free chelators are notavailable and antimicrobial potentiation is not observed. In the casewhere significant water hardness or transitional metals are available orwhere product esthetics require a specified chelator level, higherlevels may be required to allow for the availability of free,uncomplexed aminocarboxylate chelators to function asantimicrobial/preservative potentiators.

Antimicrobial Preservative

Optionally, but preferably, an antimicrobial preservative can be addedto the composition of the present invention, preferably solubilized,water-soluble, antimicrobial preservative, to protect the fabric colorcare active and/or other easily degradable organic ingredients such asnatural polysaccharides, because these molecules are made up, e.g., ofvarying numbers of glucose units which can make them a prime breedingground for certain microorganisms, especially when in aqueouscompositions. This drawback can lead to the problem of storage stabilityof fabric care solutions for any significant length of time.Contamination by certain microorganisms with subsequent microbial growthcan result in an unsightly and/or malodorous solution. Because microbialgrowth in the fabric care solutions is highly objectionable when itoccurs, it is highly preferable to include an antimicrobialpreservative, preferably solubilized, water-soluble, antimicrobialpreservative, which is effective for inhibiting and/or regulatingmicrobial growth in order to increase storage stability of thepreferably clear, aqueous odor-absorbing solution containing the fabriccolor care active.

It is preferable to use a broad spectrum preservative, e.g., one that iseffective on both bacteria (both gram positive and gram negative) andfungi. A limited spectrum preservative, e.g., one that is only effectiveon a single group of microorganisms, e.g., fungi, can be used incombination with a broad spectrum preservative or other limited spectrumpreservatives with complimentary and/or supplementary activity. Amixture of broad spectrum preservatives can also be used. In some caseswhere a specific group of microbial contaminants is problematic (such asGram negatives), aminocarboxylate chelators can be used alone or aspotentiators in conjunction with other preservatives. These chelatorswhich include, e.g., ethylenediaminetetraacetic acid (EDTA),hydroxyethylenediaminetriacetic acid, diethylenetriaminepentaaceticacid, and other aminocarboxylate chelators, and mixtures thereof, andtheir salts, and mixtures thereof, can increase preservativeeffectiveness against Gram-negative bacteria, especially Pseudomonasspecies.

Antimicrobial preservatives useful in the present invention includebiocidal compounds, i.e., substances that kill microorganisms, orbiostatic compounds, i.e., substances that inhibit and/or regulate thegrowth of microorganisms. Suitable preservatives are disclosed in U.S.Pat. Nos. 5,534,165; 5,578,563; 5,663,134; 5,668,097; 5,670,475; and5,714,137, Trinh et al. issued Jul. 9, 1996; Nov. 26, 1996; Sep. 2,1997; Sep. 16, 1997; Sep. 23, 1997; and Feb. 3, 1998 respectively, allof said patents being incorporated hereinbefore by reference. Manyantimicrobial preservatives are given under the section on AntimicrobialActive given herein above. Water insoluble antimicrobial preservativessuch as paraben and triclosan are useful in the fabric care compositionsof the present invention, but they require the use of a solubilizer, anemulsifier, a dispersing agent, or the like, such as a surfactant and/orcyclodextrin to effectively distribute said preservative in the liquidcomposition. Preferred antimicrobial preservative are those that arewater-soluble and are effective at low levels. Water-solublepreservatives useful in the present invention are those that have asolubility in water of at least about 0.3 g per 100 ml of water, i.e.,greater than about 0.3% at room temperature, preferably greater thanabout 0.5% at room temperature.

The water-soluble antimicrobial preservative in the present invention isincluded at an effective amount. The term “effective amount” as hereindefined means a level sufficient to prevent spoilage, or prevent growthof inadvertently added microorganisms, for a specific period of time. Inother words, the preservative is not being used to kill microorganismson the surface onto which the composition is deposited in order toeliminate odors produced by microorganisms. Instead, it is preferablybeing used to prevent spoilage of the fabric color care active solutionin order to increase the shelf-life of the composition. Preferred levelsof preservative are from about 0.0001% to about 0.5%, more preferablyfrom about 0.0002% to about 0.2%, most preferably from about 0.0003% toabout 0.1%, by weight of the usage composition.

The preservative can be any organic preservative material which will notcause damage to fabric appearance, e.g., discoloration, coloration,bleaching. Preferred water-soluble preservatives include organic sulfurcompounds, halogenated compounds, cyclic organic nitrogen compounds, lowmolecular weight aldehydes, quaternary ammonium compounds, dehydroaceticacid, phenyl and phenolic compounds, and mixtures thereof.

The preservatives of the present invention can be used in mixtures inorder to control a broad range of microorganisms.

Bacteriostatic effects can sometimes be obtained for aqueouscompositions by adjusting the composition pH to an acid pH, e.g., lessthan about pH 4, preferably less than about pH 3, or a basic pH, e.g.,greater than about 10, preferably greater than about 11.

Antistatic Agents

The composition of the present invention can optionally contain aneffective amount of antistatic agent to provide the treated clothes within-wear static. Preferred antistatic agents are those that are watersoluble in at least an effective amount, such that the compositionremains a clear solution. Examples of these antistatic agents aremonoalkyl cationic quaternary ammonium compounds, e.g., mono(C₁₀-C₁₄alkyl)trimethyl ammonium halide, such as monolauryl trimethyl ammoniumchloride, hydroxycetyl hydroxyethyl dimethyl ammonium chloride,available under the trade name Dehyquart E® from Henkel, and ethylbis(polyethoxy ethanol) alkylammonium ethylsulfate, available under thetrade name Variquat 66® from Witco Corp., polyethylene glycols,polymeric quaternary ammonium salts, such as polymers conforming to thegeneral formula:—[N(CH₃)₂—(CH₂)₃—NH—CO—NH—(CH₂)₃—N(CH₃)₂ ⁺—CH₂CH₂OCH₂CH₂]—_(x) ²⁺2x[Cl⁻]available under the trade name Mirapol A-15® from Rhône-Poulenc, and—[N(CH₃)₂—(CH₂)₃—NH—CO—(CH₂)₄—CO—NH—(CH₂)₃—N(CH₃)₂—(CH₂CH₂OCH₂CH₂]—_(x)^(+ x)[Cl⁻],available under the trade name Mirapol AD-1® from Rhône-Polenc,quaternized polyethyleneimines,vinylpyrrolidone/methacrylamidopropyltrimethylammonium chloridecopolymer, available under the trade name Gafquat HS-100® from GAF;triethonium hydrolyzed collagen ethosulfate, available under the tradename Quat-Pro E® from Maybrook; and mixtures thereof.

It is preferred that a no foaming, or low foaming, agent is used, toavoid foam formation during fabric treatment. It is also preferred thatpolyethoxylated agents such as polyethylene glycol or Variquat 66® arenot used when alpha-cyclodextrin is used. The polyethoxylate groups havea strong affinity to, and readily complex with, alpha-cyclodextrin whichin turn depletes the uncomplexed cyclodextrin available for odorcontrol.

When an antistatic agent is used it is typically present at a level offrom about 0.05% to about 10%, preferably from about 0.1% to about 5%,more preferably from about 0.3% to about 3%, by weight of the usagecomposition.

Insect and/or Moth Repelling Agent

The composition of the present invention can optionally contain aneffective amount of insect and/or moth repelling agents. Typical insectand moth repelling agents are pheromones, such as anti-aggregationpheromones, and other natural and/or synthetic ingredients. Preferredinsect and moth repellent agents useful in the composition of thepresent invention are perfume ingredients, such as citronellol,citronellal, citral, linalool, cedar extract, geranium oil, sandalwoodoil, 2-(diethylphenoxy)ethanol, 1-dodecene, etc. Other examples ofinsect and/or moth repellents useful in the composition of the presentinvention are disclosed in U.S. Pat. Nos. 4,449,987, 4,693,890,4,696,676, 4,933,371, 5,030,660, 5,196,200, and in “Semio Activity ofFlavor and Fragrance Molecules on Various Insect Species”, B. D.Mookherjee et al., published in Bioactive Volatile Compounds fromPlants, ASC Symposium Series 525, R. Teranishi, R. G. Buttery, and H.Sugisawa, 1993, pp. 35-48, all of aid patents and publications beingincorporated herein by reference. When an insect and/or moth repellentis used it is typically present at a level of from about 0.005% to about3%, by weight of the usage composition.

Optional Anti-Clogging Agent

Optional anti-clogging agent which enhances the wetting andanti-clogging properties of the composition, especially when starch ispresent, is chosen from the group of polymeric glycols of alkanes andolefins having from 2 to about 6, preferably 2 carbon atoms. Theanti-clogging agent inhibits the formation of “plugs” in the spraynozzle. An example of the preferred anti-clogging agent is polyethyleneglycol having an average molecular weight of from about 800 to about12,000, more preferably from about 1,400 to about 8,000. When used, theanti-clogging agent is present at a level of from about 0.01% to about1%, preferably from about 0.05% to about 0.5%, more preferably, fromabout 0.1% to about 0.3% by weight of the usage composition.

Aqueous Carrier

The preferred carrier of the present invention is water. The water whichis used can be distilled, deionized, or tap water. Water is the mainliquid carrier due to its low cost, availability, safety, andenvironmental compatibility. Water serves as the liquid carrier for thefabric color care active and other soluble and/or dispersible optionalingredients.

The level of liquid carrier in the compositions of the present inventionis typically greater than about 80%, preferably greater than about 90%,more preferably greater than about 95, by weight of the composition.When a concentrated composition is used, the level of liquid carrier istypically from about 2% to about 98%, by weight of the composition,preferably from about 35% to about 97%, more preferably from about 60%to about 95%, by weight of the composition.

Optionally, in addition to water, the carrier can contain a lowmolecular weight organic solvent that is highly soluble in water, e.g.,ethanol, propanol, isopropanol, and the like, and mixtures thereof. Lowmolecular weight alcohols can help the treated fabric to dry faster. Theoptional solvent is also useful in the solubilization of some shaperetention polymers described hereinbefore. The optional water solublelow molecular weight solvent can be used at a level of up to about 50%,typically from about 0.1% to about 25%, preferably from about 2% toabout 15%, more preferably from about 5% to and 10%, by weight of thetotal composition. Factors that need to consider when a high level ofsolvent is used in the composition are odor, flammability, andenvironment impact.

II. ARTICLE OF MANUFACTURE

The present invention can also be comprise an article of manufacturecomprising said composition plus a spray dispenser. Preferably thearticles of manufacture are in association with a set of instructionsfor how to use the composition to treat fabrics correctly so as toprovide good color, especially one step color restoration, including,e.g., the manner and/or amount of composition to spray, and thepreferred ways of handling of the fabrics, as will be described withmore detailed herein below where wrinkle control is also desired. It isimportant that the instructions be as simple and clear as possible, sothat using pictures and/or icons is desirable.

Spray Dispenser

The article of manufacture herein comprises a spray dispenser. Thefabric color care composition is placed into a spray dispenser in orderto be distributed onto the fabric. Said spray dispenser for producing aspray of liquid droplets can be any of the manually activated means asis known in the art, e.g. trigger-type, pump-type, non-aerosolself-pressurized, and aerosol-type spray means, for adding the fabriccolor care compositions to small fabric surface areas and/or a smallnumber of garments, as well as non-manually operated, powered sprayersfor conveniently adding the fabric color care composition to largefabric surface areas and/or a large number of garments. The spraydispenser herein does not normally include those that will substantiallyfoam the clear, aqueous fabric color care composition. It has been foundthat the performance is improved by providing smaller particle droplets.Desirably the Sauter mean particle diameter is from about 10 μm to about120 μm, more preferably, from about 20 μm to about 100 μm. Dewrinklingbenefits are improved by providing small particles (droplets), asdiscussed hereinbefore, especially when the surfactant is present.

The spray dispenser can be an aerosol dispenser. Said aerosol dispensercomprises a container which can be constructed of any of theconventional materials employed in fabricating aerosol containers. Thedispenser must be capable of withstanding internal pressure in the rangeof from about 20 to about 110 p.s.i.g., more preferably from about 20 toabout 70 p.s.i.g. The one important requirement concerning the dispenseris that it be provided with a valve member which will permit the clear,aqueous de-wrinkle composition contained in the dispenser to bedispensed in the form of a spray of very fine, or finely divided,particles or droplets. The aerosol dispenser utilizes a pressurizedsealed container from which the clear, aqueous de-wrinkle composition isdispensed through a special actuator/valve assembly under pressure. Theaerosol dispenser is pressurized by incorporating therein a gaseouscomponent generally known as a propellant. Common aerosol propellants,e.g., gaseous hydrocarbons such as isobutane, and mixed halogenatedhydrocarbons, can be used. Halogenated hydrocarbon propellants such aschlorofluoro hydrocarbons have been alleged to contribute toenvironmental problems, and are not preferred. When cyclodextrin ispresent hydrocarbon propellants are not preferred, because they can formcomplexes with the cyclodextrin molecules thereby reducing theavailability of uncomplexed cyclodextrin molecules for odor adsorption.Preferred propellants are compressed air, nitrogen, inert gases, carbondioxide, etc. A more complete description of commercially availableaerosol-spray dispensers appears in U.S. Pat. No. 3,436,772, Stebbins,issued Apr. 8, 1969; and U.S. Pat. No. 3,600,325, Kaufman et al., issuedAug. 17, 1971; both of said references are incorporated herein byreference.

Preferably the spray dispenser can be a self-pressurized non-aerosolcontainer having a convoluted liner and an elastomeric sleeve. Saidself-pressurized dispenser comprises a liner/sleeve assembly containinga thin, flexible radially expandable convoluted plastic liner of fromabout 0.010 to about 0.020 inch thick, inside an essentially cylindricalelastomeric sleeve. The liner/sleeve is capable of holding a substantialquantity of fabric color care composition product and of causing saidproduct to be dispensed. A more complete description of self-pressurizedspray dispensers can be found in U.S. Pat. No. 5,111,971, Winer, issuedMay 12, 1992, and U.S. Pat. No. 5,232,126, Winer, issued Aug. 3, 1993;both of said references are herein incorporated by reference. Anothertype of aerosol spray dispenser is one wherein a barrier separates thefabric color care composition from the propellant (preferably compressedair or nitrogen), as disclosed in U.S. Pat. No. 4,260,110, issued Apr.7, 1981, and incorporated herein by reference. Such a dispenser isavailable from EP Spray Systems, East Hanover, N.J.

More preferably, the spray dispenser is a non-aerosol, manuallyactivated, pump-spray dispenser. Said pump-spray dispenser comprises acontainer and a pump mechanism which securely screws or snaps onto thecontainer. The container comprises a vessel for containing the aqueousfabric color care composition to be dispensed.

The pump mechanism comprises a pump chamber of substantially fixedvolume, having an opening at the inner end thereof. Within the pumpchamber is located a pump stem having a piston on the end thereofdisposed for reciprocal motion in the pump chamber. The pump stem has apassageway there through with a dispensing outlet at the outer end ofthe passageway and an axial inlet port located inwardly thereof.

The container and the pump mechanism can be constructed of anyconventional material employed in fabricating pump-spray dispensers,including, but not limited to: polyethylene; polypropylene;polyethyleneterephthalate; blends of polyethylene, vinyl acetate, andrubber elastomer. A preferred container is made of clear, e.g.,polyethylene terephthalate. Other materials can include stainless steel.A more complete disclosure of commercially available dispensing devicesappears in: U.S. Pat. No. 4,895,279, Schultz, issued Jan. 23, 1990; U.S.Pat. No. 4,735,347, Schultz et al., issued Apr. 5, 1988; and U.S. Pat.No. 4,274,560, Carter, issued Jun. 23, 1981; all of said references areherein incorporated by reference.

Most preferably, the spray dispenser is a manually activatedtrigger-spray dispenser. Said trigger-spray dispenser comprises acontainer and a trigger both of which can be constructed of any of theconventional material employed in fabricating trigger-spray dispensers,including, but not limited to: polyethylene; polypropylene; polyacetal;polycarbonate; polyethyleneterephthalate; polyvinyl chloride;polystyrene; blends of polyethylene, vinyl acetate, and rubberelastomer. Other materials can include stainless steel and glass. Apreferred container is made of clear, e.g. polyethylene terephthalate.The trigger-spray dispenser does not incorporate a propellant gas intothe odor-absorbing composition, and preferably it does not include thosethat will foam the fabric color care composition. The trigger-spraydispenser herein is typically one which acts upon a discrete amount ofthe fabric color care composition itself, typically by means of a pistonor a collapsing bellows that displaces the composition through a nozzleto create a spray of thin liquid. Said trigger-spray dispenser typicallycomprises a pump chamber having either a piston or bellows which ismovable through a limited stroke response to the trigger for varying thevolume of said pump chamber. This pump chamber or bellows chambercollects and holds the product for dispensing. The trigger spraydispenser typically has an outlet check valve for blocking communicationand flow of fluid through the nozzle and is responsive to the pressureinside the chamber. For the piston type trigger sprayers, as the triggeris compressed, it acts on the fluid in the chamber and the spring,increasing the pressure on the fluid. For the bellows spray dispenser,as the bellows is compressed, the pressure increases on the fluid. Theincrease in fluid pressure in either trigger spray dispenser acts toopen the top outlet check valve. The top valve allows the product to beforced through the swirl chamber and out the nozzle to form a dischargepattern. An adjustable nozzle cap can be used to vary the pattern of thefluid dispensed.

For the piston spray dispenser, as the trigger is released, the springacts on the piston to return it to its original position. For thebellows spray dispenser, the bellows acts as the spring to return to itsoriginal position. This action causes a vacuum in the chamber. Theresponding fluid acts to close the outlet valve while opening the inletvalve drawing product up to the chamber from the reservoir.

A more complete disclosure of commercially available dispensing devicesappears in U.S. Pat. No. 4,082,223, Nozawa, issued Apr. 4, 1978; U.S.Pat. No. 4,161,288, McKinney, issued Jul. 17, 1985; U.S. Pat. No.4,434,917, Saito et al., issued Mar. 6, 1984; and U.S. Pat. No.4,819,835, Tasaki, issued Apr. 11, 1989; U.S. Pat. No. 5,303,867,Peterson, issued Apr. 19, 1994; all of said references are incorporatedherein by reference.

A broad array of trigger sprayers or finger pump sprayers are suitablefor use with the compositions of this invention. These are readilyavailable from suppliers such as Calmar, Inc., City of Industry, Calif.;CSI (Continental Sprayers, Inc.), St. Peters, Miss.; Berry PlasticsCorp., Evansville, Ind., a distributor of Guala® sprayers; or SeaquestDispensing, Cary, Ill.

The preferred trigger sprayers are the blue inserted Guala® sprayer,available from Berry Plastics Corp., or the Calmar TS800-1A®, TS1300®,and TS-800-2®, available from Calmar Inc., because of the fine uniformspray characteristics, spray volume, and pattern size. More preferredare sprayers with precompression features and finer spraycharacteristics and even distribution, such as Yoshino sprayers fromJapan. Any suitable bottle or container can be used with the triggersprayer, the preferred bottle is a 17 fl-oz. bottle (about 500 ml) ofgood ergonomics similar in shape to the Cinch® bottle. It can be made ofany materials such as high density polyethylene, polypropylene,polyvinyl chloride, polystyrene, polyethylene terephthalate, glass, orany other material that forms bottles. Preferably, it is made of highdensity polyethylene or clear polyethylene terephthalate.

For smaller fluid ounce sizes (such as 1 to 8 ounces), a finger pump canbe used with canister or cylindrical bottle. The preferred pump for thisapplication is the cylindrical Euromist II® from Seaquest Dispensing.More preferred are those with precompression features.

The article of manufacture herein preferably can also comprise anon-manually operated spray dispenser. By “non-manually operated” it ismeant that the spray dispenser can be manually activated, but the forcerequired to dispense the fabric color care composition is provided byanother, non-manual means. Non-manually operated sprayers include, butare not limited to, powered sprayers, air aspirated sprayers, liquidaspirated sprayers, electrostatic sprayers, and nebulizer sprayers. Thefabric color care composition is placed into a spray dispenser in orderto be distributed onto the fabric.

Powered sprayers include self contained powered pumps that pressurizethe aqueous de-wrinkle composition and dispense it through a nozzle toproduce a spray of liquid droplets. Powered sprayers are attacheddirectly or remotely through the use of piping/tubing to a reservoir(such as a bottle) to hold the aqueous fabric color care composition.Powered sprayers can include, but are not limited to, centrifugal orpositive displacement designs. It is preferred that the powered sprayerbe powered by a portable DC electrical current from either disposablebatteries (such as commercially available alkaline batteries) orrechargeable battery units (such as commercially available nickelcadmium battery units). Powered sprayers can also be powered by standardAC power supply available in most buildings. The discharge nozzle designcan be varied to create specific spray characteristics (such as spraydiameter and particle size). It is also possible to have multiple spraynozzles for different spray characteristics. The nozzle may or may notcontain an adjustable nozzle shroud that would allow the spraycharacteristics to be altered.

Nonlimiting examples of commercially available powered sprayers aredisclosed in U.S. Pat. No. 4,865,255, Luvisotto, issued Sep. 12, 1989which is incorporated herein by reference. Preferred powered sprayersare readily available from suppliers such as Solo, Newport News, Va.(e.g., Solo Spraystar™ rechargeable sprayer, listed as manual part #: US460 395) and Multi-sprayer Systems, Minneapolis, Minn. (e.g., model:Spray 1).

Air aspirated sprayers include the classification of sprayersgenerically known as “air brushes”. A stream of pressurized air draws upthe aqueous fabric color care composition and dispenses it through anozzle to create a spray of liquid. The fabric color care compositioncan be supplied via separate piping/tubing or more commonly is containedin a jar to which the aspirating sprayer is attached.

Nonlimiting examples of commercially available air aspirated sprayersappears in U.S. Pat. No. 1,536,352, Murray, issued Apr. 22, 1924 andU.S. Pat. No. 4,221,339, Yoshikawa, issues Sep. 9, 1980; all of saidreferences are incorporated herein by reference. Air aspirated sprayersare readily available from suppliers such as The Badger Air-Brush Co.,Franklin Park, Ill. (e.g., model #: 155) and Wilton Air Brush Equipment,Woodridge, Ill. (e.g., stock #: 415-4000, 415-4001, 415-4100).

Liquid aspirated sprayers are typical of the variety in widespread useto spray garden chemicals. The aqueous dewrinkling composition is drawninto a fluid stream by means of suction created by a Venturi effect. Thehigh turbulence serves to mix the aqueous fabric color care compositionwith the fluid stream (typically water) in order to provide a uniformmixture/concentration. It is possible with this method of delivery todispense the aqueous concentrated fabric color care composition of thepresent invention and then dilute it to a selected concentration withthe delivery stream.

Liquid aspirated sprayers are readily available from suppliers such asChapin Manufacturing Works, Batavia, N.Y. (e.g., model #: 6006).

Electrostatic sprayers impart energy to the aqueous dewrinklingcomposition via a high electrical potential. This energy serves toatomize and charge the aqueous fabric color care composition, creating aspray of fine, charged particles. As the charged particles are carriedaway from the sprayer, their common charge causes them to repel oneanother. This has two effects before the spray reaches the target.First, it expands the total spray mist. This is especially importantwhen spraying to fairly distant, large areas. The second effect ismaintenance of original particle size. Because the particles repel oneanother, they resist collecting together into large, heavier particleslike uncharged particles do. This lessens gravity's influence, andincreases the charged particle reaching the target. As the mass ofnegatively charged particles approach the target, they push electronsinside the target inwardly, leaving all the exposed surfaces of thetarget with a temporary positive charge. The resulting attractionbetween the particles and the target overrides the influences of gravityand inertia. As each particle deposits on the target, that spot on thetarget becomes neutralized and no longer attractive. Therefore, the nextfree particle is attracted to the spot immediately adjacent and thesequence continues until the entire surface of the target is covered.Hence, charged particles improve distribution and reduce drippage.

Nonlimiting examples of commercially available electrostatic sprayersappears in U.S. Pat. No. 5,222,664, Noakes, issued Jun. 29, 1993; U.S.Pat. No. 4,962,885, Coffee, issued Oct. 16, 1990; U.S. Pat. No.2,695,002, Miller, issued November 1954; U.S. Pat. No. 5,405,090,Greene, issued Apr. 11, 1995; U.S. Pat. No. 4,752,034, Kuhn, issued Jun.21, 1988; U.S. Pat. No. 2,989,241, Badger, issued June 1961; all of saidpatents are incorporated herein by reference. Electrostatic sprayers arereadily available from suppliers such as Tae In Tech Co, South Korea andSpectrum, Houston, Tex.

Nebulizer sprayers impart energy to the aqueous dewrinkling compositionvia ultrasonic energy supplied via a transducer. This energy results inthe aqueous fabric color care compositions to be atomized. Various typesof nebulizers include, but are not limited to, heated, ultrasonic, gas,venturi, and refillable nebulizers.

Nonlimiting examples of commercially available nebulizer sprayersappears in U.S. Pat. No. 3,901,443, Mitsui, issued Aug. 26, 1975; U.S.Pat. No. 2,847,248, Schmitt, issued August 1958; U.S. Pat. No.5,511,726, Greenspan, issued Apr. 30, 1996; all of said patents areincorporated herein by reference. Nebulizer sprayers are readilyavailable from suppliers such as A&D Engineering, Inc., Milpitas, Calif.(e.g., model A&D Un-231 ultrasonic handy nebulizer) and Amici, Inc.,Spring City, Pa. (model: swirler nebulizer).

The preferred article of manufacture herein comprises a non-manuallyoperated sprayer, such as a battery-powered sprayer, containing theaqueous fabric color care composition. More preferably the article ofmanufacture comprises a combination of a non-manually operated sprayerand a separate container of the aqueous fabric color care composition,to be added to the sprayer before use and/or to be separated forfilling/refilling. The separate container can contain an usagecomposition, or a concentrated composition to be diluted before use,and/or to be used with a diluting sprayer, such as with a liquidaspirated sprayer, as described herein above.

Also, as described hereinbefore, the separate container should havestructure that mates with the rest of the sprayer to ensure a solid fitwithout leakage, even after motion, impact, etc. and when handled byinexperienced consumers. The sprayer desirably can also have anattachment system that is safe and preferably designed to allow for theliquid container to be replaced by another container that is filled.E.g., the fluid reservoir can be replaced by a filled container. Thiscan minimize problems with filling, including minimizing leakage, if theproper mating and sealing means are present on both the sprayer and thecontainer. Desirably, the sprayer can contain a shroud to ensure properalignment and/or to permit the use of thinner walls on the replacementcontainer. This minimizes the amount of material to be recycled and/ordiscarded. The package sealing or mating system can be a threadedclosure (sprayer) which replaces the existing closure on the filled andthreaded container. A gasket is desirably added to provide additionalseal security and minimize leakage. The gasket can be broken by actionof the sprayer closure. These threaded sealing systems can be based onindustry standards. However, it is highly desirable to use a threadedsealing system that has non-standard dimensions to ensure that theproper sprayer/bottle combination is always used. This helps prevent theuse of fluids that are toxic, which could then be dispensed when thesprayer is used for its intended purpose.

An alternative sealing system can be based on one or more interlockinglugs and channels. Such systems are commonly referred to as “bayonet”systems. Such systems can be made in a variety of configurations, thusbetter ensuring that the proper replacement fluid is used. Forconvenience, the locking system can also be one that enables theprovision of a “child-proof” cap on the refill bottle. This“lock-and-key” type of system thus provides highly desirable safetyfeatures. There are a variety of ways to design such lock and keysealing systems.

Care must be taken, however, to prevent the system from making thefilling and sealing operation too difficult. If desired, the lock andkey can be integral to the sealing mechanism. However, for the purposeof ensuring that the correct recharge or refill is used, theinterlocking pieces can be separate from the sealing system. E.g., theshroud and the container could be designed for compatibility. In thisway, the unique design of the container alone could provide therequisite assurance that the proper recharge/refill is used.

Examples of threaded closures and bayonet systems can be found in U.S.Pat. No. 4,781,311, Nov. 1, 1988 (Angular Positioned Trigger Sprayerwith Selective Snap-Screw Container Connection, Clorox), U.S. Pat. No.5,560,505, Oct. 1, 1996 (Container and Stopper Assembly Locked Togetherby Relative Rotation and Use Thereof, Cebal SA), and U.S. Pat. No.5,725,132, Mar. 10, 1998 (Dispenser with Snap-Fit Container Connection,Centico International). All of said patents are incorporated herein byreference.

III. METHOD OF USE

The fabric color care composition, which contains a fabric color careactive, and optionally, e.g., perfume, odor control agent includingcyclodextrin, antimicrobial actives and/or preservative, surfactant,antioxidant, metal chelating agent including aminocarboxylate chelatingagent, antistatic agent, insect and moth repelling agent, fabricsoftener active, dye transfer inhibiting agent, brightener, soil releaseagent, dispersant, suds suppressor, and mixtures thereof, can be used bydistributing, e.g., by placing, an effective amount of the aqueoussolution onto the fabric surface or fabric article to be treated.Distribution can be achieved by using a spray device, a roller, a pad,etc., preferably a spray dispenser. For wrinkle control, for wrinkleremoval, an effective amount means an amount sufficient to remove ornoticeably reduce the appearance of wrinkles on fabric. Preferably, theamount of fabric care solution is not so much as to saturate or create apool of liquid on said article or surface and so that when dry there isno visual deposit readily discernible.

An effective amount of the liquid composition of the present inventionis preferably sprayed onto fabric and/or fabric articles. When thecomposition is sprayed onto fabric, an effective amount should bedeposited onto the fabric, with the fabric becoming damp or totallysaturated with the composition, typically from about 5% to about 150%,preferably from about 10% to about 100%, more preferably from about 20%to about 75%, by weight of the fabric. The treated fabric typically hasfrom about 0.005% to about 4%, preferably from about 0.01% to about 2%,more preferably from about 0.05% to about 1%, by weight of the fabric ofsaid fabric color care active. Once the fabric has been sprayed, it ishung until dry. It is preferable that the treatment is performed inaccordance with the instructions for use, to ensure that the consumerknows what benefits can be achieved, and how best to obtain thesebenefits.

Since the treatment of the worn, faded fabric necessarily changes theintensity of the fabric color, it is essential that the treatment needsto be uniform, either by fully treated the fabric surface with thefabric color care composition, or by uniformly spraying the fabricsurface with small droplets of the composition, so that visually thecolor improvement appears uniform. In other words, preferably, thefabric color care composition is applied uniformly to the entire visiblesurface of the fabric. Thus, it is preferable that the treatment isperformed in accordance with an instruction for use, to ensure that thefabric needs to be applied uniformly to achieve the optimal colorrestoration and/or rejuvenation benefit.

The spraying means should be capable of providing droplets with a weightaverage diameter of from about 5 μm to about 250 μm, preferably fromabout 8 μm to about 120 μm, more preferably from about 10 μm to about 80μm. When the compositions are applied in the form of the very smallparticles (droplets), the distribution is further improved and overallperformance is also improved. The presence of the optional surfactantpromotes spreading of the solution and helps a uniform distribution ofthe fabric color care active on the fabric surface.

The fabric color care composition can also be applied to fabric via adipping and/or soaking process followed by a drying step. Theapplication can be done in consumer's home by the use of commercialproduct.

The present invention also comprises a method of using concentratedliquid or solid fabric color care compositions, which are diluted toform compositions with the usage concentrations, as given hereinabove,for use in the “usage conditions”. Concentrated compositions comprise ahigher level of fabric color care active, typically from about 1% toabout 99%, preferably from about 2% to about 65%, more preferably fromabout 3% to about 25%, by weight of the concentrated fabric color carecomposition. Concentrated compositions are used in order to provide aless expensive product per use. The concentrated product is preferablydiluted with about 50% to about 10,000%, more preferably from about 50%to about 8,000%, and even more preferably from about 50% to about5,000%, by weight of the composition, of water.

The compositions of the present invention can also be used as ironingaids. An effective amount of the composition can be sprayed onto fabricand the fabric is ironed at the normal temperature at which it should beironed. The fabric can either be sprayed with an effective amount of thecomposition, allowed to dry and then ironed, or sprayed and ironedimmediately.

In a still further aspect of the invention, the composition can besprayed onto fabrics in an enclosed chamber containing the fabric to bede-wrinkled and/or treated for the color restoration/rejuvenationbenefit, thereby providing ease of operation. Examples of an enclosedchamber include a closed flexible bag, such as a plastic bag which issimilar to a garment bag, preferably with a flexible opening which canbe zipped up, or a cabinet or similar apparatus, with a door hingedlyattached. Any spraying mechanism can be used to apply the fabric colorcare composition to fabrics. A preferred distribution of the garmentcare composition is achieved by using a fog form. The mean particulatediameter size of the fabric color care composition fog is preferablyfrom about 3 microns to about 50 microns, more preferably from about 5microns to about 30 microns, and most preferably from about 10 micronsto about 20 microns.

Another aspect of the present invention is the method of using anaqueous or solid, preferably powder, fabric color care composition fortreating fabric in the rinse step, comprising an effective amount ofsaid fabric color care active, and optionally, perfume, fabric softeneractive, chlorine scavenging agent, dye transfer inhibiting agent,chemical stabilizer including antioxidant, antimicrobial actives and/orpreservative, chelating agent, aminocarboxylate chelating agent,brighteners, soil release agents or mixtures thereof. The rinse watershould contain typically from about 0.0005% to about 1%, preferably fromabout 0.0008% to about 0.1%, more preferably from about 0.001% to about0.02% of the fabric color care active.

The present invention also relates to a method for treating fabric inthe drying step, comprising an effective amount of said fabric colorcare active, and optionally, perfume, fabric softener active, dyetransfer inhibiting agents, dye fixing agent, chemical stabilizerincluding antioxidant, antimicrobial active and/or preservative,aminocarboxylate chelating agent, brightener, soil release agent, andmixtures thereof. A preferred method comprises the treatment of worn,faded fabrics with a fabric color care composition dispensed from asprayer at the beginning and/or during the drying cycle. It ispreferable that the treatment is performed in accordance with theinstructions for use, to ensure that the consumer knows what benefitscan be achieved, and how best to obtain these benefits.

All percentages, ratios, and parts herein, in the Specification,Examples, and Claims are by weight and are the normal approximationsunless otherwise stated.

The following are examples of the instant composition. The followingcompositions are prepared by mixing and dissolving the ingredients intoclear or translucent solutions.

EXAMPLE I

Ia Ib Ic Id Ie If Ingredients Wt. % Wt. % Wt. % Wt. % Wt. % Wt. %Arabinogalac- 1 — — — — — tan A⁽¹⁾ Arabinogalac- — 0.7 — — 0.5 — tanB⁽²⁾ Arabinogalac- — — 0.5 — — 0.5 tan C⁽³⁾ Curdlan⁽⁴⁾ — — — 1 — —Dextran⁽⁵⁾ — — — — 0.8 — Carrageenan — — — — — 1 Perfume 0.1 0.05 0.070.1 0.05 0.05 Polysorbate 0.2 0.1 0.15 0.2 0.1 0.1 60⁽⁶⁾ Kathon CG 3 ppm3 ppm 3 ppm 3 ppm 3 ppm 3 ppm Deionized Bal. Bal. Bal. Bal. Bal. Bal.Water ⁽¹⁾Arabinogalactan fraction that has the average molecular weightof from about 16,000 to about 20,000. ⁽²⁾Arabinogalactan fraction thathas the average molecular weight of about 100,000. ⁽³⁾Arabinogalactanfraction that has the average molecular weight of from about 10,000 toabout 150,000. ⁽⁴⁾Average molecular weight of about 72,000. ⁽⁵⁾Averagemolecular weight of about 40,000. ⁽⁶⁾A mixture of stearate esters ofsorbitol and sorbitol anhydride, consisting predominantly of themonoester, condensed with about 20 moles of ethylene oxide.

EXAMPLE II

IIa IIb IIc IId IIe IIf Ingredients Wt. % Wt. % Wt. % Wt. % Wt. % Wt. %Arabinogalac- 5 — — 5   — — tan A⁽¹⁾ Arabinogalac- — 15 — — 15   — tanB⁽²⁾ Arabinogalac- — — 25 — — 25   tan C⁽³⁾ Perfume — — — 0.3 1   1.5Polysorbate — — — 0.5 1.5 3   60 Kathon CG 5 ppm 5 ppm 10 ppm 5 ppm 5ppm 10 ppm Deionized Bal. Bal. Bal. Bal. Bal. Bal. Water

EXAMPLE III

IIIa IIIb Ingredients Wt. % Wt. % Silwet L-7001 1 — Silwet L-7200 — 0.8Perfume C 0.05 0.1 Polysorbate 60 0.1 0.2 Kathon CG 3 ppm 3 ppmDeionized Water Bal. Bal.

EXAMPLE IV

IVa IVb IVc Ingredients Wt. % Wt. % Wt. % Copolymer A⁽⁷⁾ 0.7 — —Copolymer B⁽⁸⁾ — 0.8 — Silicone Emulsion A⁽⁹⁾ — — 3 Perfume 0.06 0.050.05 Polysorbate 60 0.1 0.1 0.1 Silwet L-7602 0.5 — — Kathon CG 3 ppm 3ppm 3 ppm Deionized Water Bal. Bal. Bal. ⁽⁷⁾Acrylic acid/tert-butylacrylate copolymer, with an approximate acrylic acid/tert-butyl acrylateweight ratio of about 25/75 and an average molecular weight of fromabout 70,000 to about 100,000. ⁽⁸⁾Acrylic acid/tert-butyl acrylatecopolymer, with an approximate acrylic acid/tert-butyl acrylate weightratio of about 35/65 and an average molecular weight of from about60,000 to about 90,000. ⁽⁹⁾DC-2-5932 silicone microemulsion (25% active)from Dow Corning, with a particle size of about 24 nm, a cationicsurfactant system, and a silicone with an internal phase viscosity ofabout 1,200 cps.

EXAMPLE V

Va Vb Vc Vd Ve Ingredients Wt. % Wt. % Wt. % Wt. % Wt. % ArabinogalactanA⁽¹⁾ 1.2 — — — 5   Copolymer E⁽¹⁰⁾ — 0.5 — — — Copolymer F⁽¹¹⁾ 0.2 — 0.5— — Copolymer G⁽¹²⁾ — — — 0.5 — PDMS 10,000 cst — — — 0.3 — SiliconeEmulsion B⁽¹³⁾ — — 1   — 2   Perfume — —  0.04 — 0.5 Polysorbate 60 0.10.1 — 0.1 0.5 Neodol 23-3 —  0.25 — 0.2 — Neodol 25-3 0.2 — 0.6 — 0.3Silwet L-77 0.6 0.7 — 1   — Silwet L-7604 — — 0.5 — — Kathon CG 3 ppm 3ppm 3 ppm 3 ppm 3 ppm Deionized Water Bal. Bal. Bal. Bal. Bal.⁽¹⁰⁾Silicone-containing copolymer having t-butyl acrylate/acrylicacid/(polydimethylsiloxane macromer, 10,000 approximate molecularweight) monomer at an approximate 63/20/17 weight ratio, and of anaverage molecular weight of about 130,000. ⁽¹¹⁾Silicone-containingcopolymer having t-butylacrylate/acrylic acid/(polydimethylsiloxanemacromer, 10,000 approximate molecular weight) monomer at an approximate65/25/10 weight ratio, and of average molecular weight of about 200,000.⁽¹²⁾Silicone-containing copolymer having (N,N,N-trimethylammonioethylmethacrylate chloride)/N,N-dimethylacrylamide/(PDMS macromer - 15,000approximate molecular weight) at an approximate 40/40/20 weight ratio,and of average molecular weight of about 150,000. ⁽¹³⁾DC-1550 siliconemicroemulsion (25% active) from Dow Corning, with a particle size ofabout 50 nm, an anionic/nonionic surfactant system, and a silicone withan internal phase viscosity of about 100,000 cps.

VI Ingredients Wt % GE 176-12669 Silicone Emulsion (1) 1.43 GE SM 2658Silicone Emulsion (2) 1.43 Polyvinyl alcohol (3) 0.065 Glycerin 0.01Kathon CG 3 ppm Perfume 0.1 Distilled water Bal. (1) Cationic emulsionof hydroxy silicone, about 35% active. (2) Cationic emulsion ofamino-functional silicone, about 35% active. (3) Weight averagemolecular weight range from about 18,000 to about 27,000.

The compositions of Examples I to VI (diluted when appropriate) aresprayed onto worn, faded color clothing using, e.g., the TS-800 sprayerfrom Calmar, and allowed to evaporate off of the clothing.

The compositions of Examples I to VI (diluted when appropriate) aresprayed onto worn, faded color clothing, using a blue inserted Guala®trigger sprayer, available from Berry Plastics Corp. and a cylindricalEuromist II® pump sprayer available from Seaquest Dispensing,respectively, and allowed to evaporate off of the clothing.

The compositions of Examples I to VI (diluted when appropriate)contained in rechargeable battery-operated Solo Spraystar sprayers aresprayed onto large worn, faded color fabric surfaces of fabric, i.e.,several pieces of clothing, and allowed to evaporate off of thesesurfaces. The level of coverage is uniform and the ease and convenienceof application is superior to conventional manually operated triggersprayers.

The compositions of Examples I to VI (diluted when appropriate) are usedfor soaking or dipping of worn, faded color fabrics which are thenoptionally wrung or squeezed to remove excess liquid and subsequentlydried.

1. A method for restoring and/or rejuvenating color of a worn, fadedcolor fabric, wherein said method comprises applying an effective amountof a fabric color care active to said fabric, wherein said fabric colorcare active is selected from the group consisting of: (i)polysaccharides selected from the group consisting of:heteropolysaccharides; algal polysaccharides; microbial polysaccharides;lipopolysaccharides; fungal polysaccharides; animal polysaccharides; andmixtures thereof; (ii) water soluble and/or water dispersible syntheticpolymer selected from the group consisting of homopolymer of hydrophilicmonomers; homopolymer of hydrophobic monomers; copolymer of hydrophilicmonomers and hydrophobic monomers; and mixtures thereof; wherein saidhydrophilic monomers are selected from the group consisting of: acrylicacid; methacrylic acid; crotonic acid; maleic acid and its half esters;itaconic acid; salts of said acids; vinyl alcohol; allyl alcohol; vinylpyrrolidone; vinyl caprolactam; vinyl pyridine; vinyl imidazole; vinylsulfonate; N,N-dimethylacrylamide; N-t-butyl acrylamide; hydroxyethylmethacrylate; dimethylaminoethyl methacrylate; and mixtures thereof; andwherein said hydrophobic monomers are selected from the group consistingof: methyl acrylate; ethyl acrylate; t-butyl acrylate; methylmethacrylate; 2-ethyl hexyl methacrylate; methoxy ethyl methacrylate;vinyl acetate; vinyl propionate; vinyl neodecanoate; styrene; t-butylstyrene; vinyl toluene; methyl vinyl ether; vinyl chloride; vinylidenechloride; ethylene; propylene; other unsaturated hydrocarbons; andmixtures thereof; (iii) fabric softening actives capable of forming abilayer structure, wherein said fabric softening actives arebiodegradable and have with highly unsaturated and/or branchedhydrophobic chains; and (iv) mixtures thereof; and wherein the colorrestoration and/or rejuvenation is characterized by the ability of saidactive to change the properties of a worn, faded black cotton (chino)twill test fabric, resulting in: (A) a percentage reflectance reductionΔR of at least 3%; (B) a Hunter L value reduction ΔL of at least 0.5;and (C) a percentage pill number reduction ΔP of at least 10%.
 2. Themethod of claim 1, wherein said fabric color care active is present in afabric color care composition, and wherein said method comprisesapplying an effective amount of said composition to restore and/orrejuvenate the color of said fabric, said composition comprising: (A)said fabric color care active; (B) optionally, an effective amount toprovide olfactory effects of perfume; (C) optionally, to reduce surfacetension, and/or to improve performance and formulatability, an effectiveamount of surfactant; (D) optionally, an effective amount to absorbmalodor, of odor control agent; (E) optionally, an effective amount, tokill, or reduce the growth of microbes, of antimicrobial active; (F)optionally, an effective amount to provide improved antimicrobial actionof aminocarboxylate chelator; (G) optionally, an effective amount ofantimicrobial preservative; and (H) optionally, an aqueous carrier; saidcomposition optionally being essentially free of any material that wouldsoil or discernible when dried on the fabric surface; said compositionoptionally being substantially removed during subsequent cleaning cyclesto prevent undesirable build-up of the active on the fabrics; and saidcomposition additionally being essentially free of any material thatwould cause the treated fabric to feel sticky to the touch.
 3. Themethod of claim 2 wherein said fabric color care active is present at alevel of from about 0.05% to about 10%, by weight of said fabric carecomposition.
 4. The method of claim 2 wherein said fabric carecomposition is an aqueous composition, and is applied onto said fabricas droplets by using a spray dispenser.
 5. The method of claim 4 whereinsaid spray dispenser comprises a trigger spray device.
 6. The method ofclaim 4, wherein said spray dispenser comprises a non-manually operatedsprayer selected from the group consisting of: power sprayer; airaspirated sprayer; liquid aspirated sprayer; electrostatic sprayer; andnebulizer sprayer.
 7. The method of claim 2, wherein said fabric isdipped and/or soaked in said fabric color care composition, followed bya squeezing step and/or a drying step.
 8. The method of claim 2, whereinsaid fabric color care composition is a rinse-added compositioncontaining from about 0.1% to about 50%, by weight of the composition,of said fabric color care active.
 9. The method of claim 2, wherein saidfabric is wet, and wherein said fabric color care composition is anaqueous composition containing said fabric color care active at a levelof from about 0.01% to about 25%, by weight of the composition.
 10. Themethod of claim 9, wherein said composition is applied to said fabricfrom a spray device.
 11. The method of claim 1 wherein said fabric colorcare active comprises heteropolysaccharides, selected from the groupconsisting of acidic polysaccharides; hemicelluloses; and mixturesthereof.
 12. The method of claim 11 wherein said fabric color careactive comprises hemicelluloses, selected from the group consisting ofarabinogalactans; glucomannans, galactoglucomannans, glucuronoxylans;substituted versions thereof; derivatised versions thereof; and mixturesthereof.
 13. The method of claim 12 wherein said fabric color careactive is selected from the group consisting of arabinogalactan;substituted versions thereof; derivatised versions thereof; and mixturesthereof.
 14. The method of claim 1 wherein said fabric color care activecomprises algal polysaccharides, selected from the group consisting of:laminaran; D-xylans; D-mannans; carrageenan; agar; and mixtures thereof.15. The method of claim 1 wherein said hydrophilic monomers are selectedfrom the group consisting of: acrylic acid, methacrylic acid,N,N-dimethyl acrylamide, N,N-dimethyl methacrylamide, N-t-butylacrylamide, dimethylamino ethyl methacrylate, vinyl pyrrolidone, andmixtures thereof; and said hydrophobic monomers are selected from thegroup consisting of: methyl acrylate, methyl methacrylate, t-butylacrylate, t-butyl methacrylate, n-butyl acrylate, n-butyl methacrylate,and mixtures thereof.
 16. An article of manufacture comprising a fabriccolor care composition in a package in association with a set ofinstructions for use comprising an instruction to apply an amount ofcomposition to provide from about 0.005% to about 4% of fabric colorcare active, by weight of the fabric, to provide the color restorationand/or rejuvenation benefit, said composition comprising: (A) the fabriccolor care active of claim 1, (B) optionally, an effective amount toprovide olfactory effects of perfume; (C) optionally, to reduce surfacetension, and/or to improve performance and formulatability, an effectiveamount of surfactant; (D) optionally, an effective amount to absorbmalodor, of odor control agent; (E) optionally, an effective amount, tokill, or reduce the growth of microbes, of antimicrobial active; (F)optionally, an effective amount to provide improved antimicrobial actionof aminocarboxylate chelator; (G) optionally, an effective amount ofantimicrobial preservative; and (H) optionally, an aqueous carrier; saidcomposition optionally being essentially free of any material that wouldsoil or discernible when dried on the fabric surface; said compositionoptionally being substantially removed during subsequent cleaning cyclesto prevent undesirable build-up of the active on the fabrics; and saidcomposition additionally being essentially free of any material thatwould cause the treated fabric to feel sticky to the touch; and whereinthe color restoration and/or rejuvenation is characterized by theability of said active to change the properties of a worn, faded blackcotton chino twill test fabric resulting in: (A) a percentagereflectance reduction delta R of at least 3%, preferably at least 5%,more preferably at least 8%, and even more preferably at least 10%; (B)a Hunter L value reduction delta L of at least 0.5, preferably at least1.0, more preferably at least 1.5; and even more preferably at least 2;and (C) a percentage pill number reduction delta P of at least 10%,preferably at least 20%, more preferably at least 40%, and even morepreferably at least 80%.
 17. The article of manufacture of claim 16wherein said package comprises a spray dispenser.
 18. The article ofmanufacture of claim 17 wherein said fabric color care composition is anaqueous composition containing from about 0.1% to about 5%, by weight ofsaid composition, of said fabric color care active.
 19. The article ofmanufacture of claim 17, wherein said spray dispenser comprises anon-manually operated spray dispenser.
 20. The article of manufacture ofclaim 19 wherein said non-manually operated spray dispenser is selectedfrom the group consisting of: powered sprayer; air aspirated sprayer;liquid aspirated sprayer; electrostatic sprayer; and nebulizer sprayer.21. The article of manufacture of claim 16 wherein said set ofinstructions for use further comprises an instruction to apply saidcomposition uniformly to the entire visible surface of the fabric. 22.The method of claim 4, wherein said droplets have a weight averagediameter of from about 5 μm to about 250 μm.
 23. The method of claim 4,wherein said composition is applied uniformly to the entire visiblesurface of the fabric.
 24. The method of claim 1, wherein said fabriccolor care composition additionally contains at least one of thefollowing adjunct materials: perfume, odor control agent includingcyclodextrin, surfactant, brightener, antimicrobial active and/orantibacterial preservative, chelating agent including aminocarboxylatechelating agent, enzyme, antioxidant, static control agent, sudssuppressor, dye transfer inhibiting agent, soil release agent,dispersant, insect repelling agent, moth repelling agent, and/or liquidcarrier.
 25. The article of manufacture of claim 17, wherein said spraydispenser comprises a trigger spray device.
 26. The article ofmanufacture of claim 16, wherein said composition additionally containsat least one of the following adjunct materials: perfume, odor controlagent including cyclodextrin, surfactant, antimicrobial active and/orantibacterial preservative, metal chelating agent includingaminocarboxylate chelating agent, enzyme, static control agent, fabricsoftening active, dye transfer inhibiting agent, soil release agent,brightener, antioxidant, suds suppressor, insect repelling agent, mothrepelling agent, and/or liquid carrier.